WO2017039003A1 - Decorative sheet - Google Patents

Abstract

The purpose of the present invention is to provide a decorative sheet endowed with excellent long-term design properties and weather resistance by adding an individually vesiculated organic UV absorber and inorganic UV absorber to a topcoat layer and/or a transparent resin layer by supercritical reverse phase evaporation. A decorative sheet (1) according to an embodiment of the present invention is provided with a topcoat layer (5) in the outermost surface layer, and is provided with a transparent resin layer (4) in the underlayer of the topcoat layer (5), wherein an organic UV absorber and an inorganic UV absorber are added to the topcoat layer (5) and/or the transparent resin layer (4), and the organic UV absorber and the inorganic UV absorber are individually encapsulated in vesicles provided with an external monolayer film to yield organic UV absorber vesicles and inorganic UV absorber vesicles .

Description

Decorative sheet

The present invention relates to a decorative sheet.

For example, Patent Document 1 discloses a technique relating to a decorative sheet using an olefin-based resin that has been attracting attention as a decorative sheet replacing a vinyl chloride decorative sheet.

Japanese Patent No. 4032829

However, these decorative sheets have a problem that few of them are excellent in design and weather resistance over a long period of time.

The present invention is intended to solve such problems, and an object of the present invention is to provide a decorative sheet that is excellent in design and weather resistance over a long period of time.

In order to achieve the above object, a decorative sheet according to an aspect of the present invention is a decorative sheet including a top coat layer as an outermost layer and a transparent resin layer under the top coat layer, the top coat layer and An organic ultraviolet absorber and an inorganic ultraviolet absorber are added to at least one of the transparent resin layers, and the organic ultraviolet absorber and the inorganic ultraviolet absorber include a single layer outer film. An organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle separately encapsulated in each vesicle.

According to the decorative sheet of one embodiment of the present invention, by adding an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle to at least one of the topcoat layer and the transparent resin layer, the design property is maintained over a long period of time. It is possible to provide a decorative sheet having excellent weather resistance.

It is sectional drawing which shows the structure of the decorative sheet which concerns on 3rd Embodiment and 5th Embodiment from 1st Embodiment of this invention. It is sectional drawing which shows the structure of the decorative sheet which concerns on 4th Embodiment and 6th Embodiment of this invention.

Hereinafter, specific examples of the configuration of the decorative sheet according to the first to sixth embodiments of the present invention will be described with reference to FIGS. 1 and 2.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. In other instances, well-known structures are shown in schematic form in order to simplify the drawing. Moreover, in each figure, the same referential mark is attached | subjected to the component which exhibits the same or similar function, and the overlapping description is abbreviate | omitted. In addition, each embodiment shown below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is based on the material, shape, structure, and the like of the component parts. It is not specified to the following. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

(First embodiment)
The decorative sheet of the present embodiment is a decorative sheet provided with a top coat layer on the outermost layer and a transparent resin layer made of a transparent olefin resin under the top coat layer, the top coat layer and the transparent resin layer. At least one of these is added with an organic ultraviolet absorber and an inorganic ultraviolet absorber.

And in the decorative sheet of this embodiment, the organic ultraviolet absorber vesicle in which the organic ultraviolet absorber and the inorganic ultraviolet absorber are separately encapsulated in vesicles each having a single-layer outer film. It is important to be an inorganic ultraviolet absorber vesicle. This makes it possible to finely set the amount of organic UV absorber vesicles and inorganic UV absorber vesicles with different absorption wavelengths and lifetimes depending on the use of the decorative sheet. It is possible to provide.

As the organic ultraviolet absorber, for example, at least one selected from benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate can be used. In particular, a benzotriazole-based or triazine-based organic ultraviolet absorber has a high ultraviolet-absorbing ability and is excellent in heat resistance, volatilization resistance, and resin compatibility.

Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzo Triazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2 Examples include '-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol.
Examples of triazine-based UV absorbers include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine. 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyl) Oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2 ′ -ethyl And) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4- Methoxybenzophenone) and the like.
Examples of the benzoate UV absorber include phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, 2,4-dibenzoate, and the like. And tertiary amylphenyl-3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate, and the like. Examples of the cyanoacrylate-based ultraviolet absorber include ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Further, as the inorganic ultraviolet absorber, for example, zinc oxide, titanium oxide, ceria oxide and the like can be used. Among these, zinc oxide is preferable because it has a refractive index close to that of the transparent olefin resin and the topcoat layer resin and can maintain high transparency even when the zinc oxide is added. Note that it is preferable to use an inorganic ultraviolet absorber having a particle size in the range of 1 nm to 200 nm.

It is important that the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle of the present embodiment are prepared by a supercritical reverse phase evaporation method. Here, the supercritical reverse phase evaporation method will be described in detail. In the supercritical reverse phase evaporation method, the substance that forms the outer membrane of the vesicle is uniformly dissolved in carbon dioxide under supercritical conditions, temperature conditions above the critical point or pressure conditions above the critical point, to form a mixture, Add an organic UV absorber as a water-soluble or hydrophilic encapsulant or an aqueous phase containing an inorganic UV absorber to the mixture, and absorb organic UV as an encapsulant in a single layer (single layer) A capsule-like organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle each containing an agent or an inorganic ultraviolet absorbent are prepared. The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher. The carbon dioxide under the temperature above the critical point or under the pressure under the critical point means carbon dioxide under the condition that only the critical temperature or the critical pressure exceeds the critical condition. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained.

Examples of phospholipids that form the outer membrane of vesicles include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean Examples include glycerophospholipids such as lecithin, sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.
As a substance that forms the outer membrane of the vesicle, in addition to the phospholipid, a nonionic surfactant or a dispersant such as a mixture of this with cholesterols or triacylglycerol can be employed.

More specifically, examples of the nonionic surfactant include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene. Polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer 1 type, or 2 or more types, such as these, can be used. As cholesterols, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate or cholecalciferol can be used.

Further, the outer membrane of the vesicle may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet of the present embodiment, it is important that the outer membrane is a vesicle formed from phospholipid, and the compatibility with the resin composition that is the main component of the topcoat layer and the transparent resin layer is good. can do.

When such an organic ultraviolet absorber vesicle and an inorganic ultraviolet absorber vesicle are added to the topcoat layer, the organic ultraviolet absorber vesicle is organic to 100 parts by weight of the resin composition as the main component of the topcoat layer. It is preferable to add 0.5 to 20 parts by weight of the ultraviolet absorber vesicle and 0.5 to 20 parts by weight of the inorganic ultraviolet absorber vesicle. At this time, if the addition amount of both ultraviolet absorbers is less than 0.5 parts by weight, the effect of ultraviolet absorbing ability is low, and if it is more than 20 parts by weight, the possibility of blocking increases. More preferably, 1 to 10 parts by weight of the organic ultraviolet absorbent vesicle and 1 to 10 parts by weight of the inorganic ultraviolet absorbent vesicle are added, and still more preferably, the organic ultraviolet absorbent vesicle is added. 3 to 5 parts by weight, and 3 to 5 parts by weight of an inorganic ultraviolet absorber vesicle is added.

In addition, when added to the transparent resin layer, 0.1 to 5 parts by weight of an organic ultraviolet absorbent vesicle is added to 100 parts by weight of the resin composition that is the main component of the transparent resin layer. It is preferable to add 0.1 to 5 parts by weight of an ultraviolet absorber vesicle. At this time, if the addition amount of both UV absorbers is less than 0.1 parts by weight, the effect of UV absorbing ability is low, and if it is more than 5 parts by weight, the possibility of bleeding out increases. More preferably, 0.2 to 3 parts by weight of an organic ultraviolet absorbent vesicle and 0.2 to 3 parts by weight of an inorganic ultraviolet absorbent vesicle are added.

In the decorative sheet of the present embodiment, it is important that an embossed pattern is formed in the transparent resin layer, and that a topcoat layer is embedded at least in the concave portion of the embossed pattern. More preferably, it is preferable to form the top coat layer in the recess by wiping.

Also, it is important that an ink layer formed of an ink to which at least a light stabilizer is added is provided under the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, it is possible to suppress the fading of the pigment due to the radicals generated by the resin degradation of the ink layer binder resin itself and other layers reducing the chemical components of the pigment in the ink. .

Hereinafter, a specific configuration of the decorative sheet of the present embodiment will be described with reference to FIG.
(overall structure)
FIG. 1 shows a specific configuration of the decorative sheet 1 of the present embodiment, and is composed of a plurality of resin layers. In the decorative sheet 1 of this embodiment, a top coat layer 5, a transparent resin layer 4, an adhesive layer 7, an ink layer 3, an original fabric layer 2, a concealing layer 8 and a primer layer 6 are laminated from the surface layer side. Moreover, in order to improve designability, the embossed pattern 4a is formed in the surface at the side of the topcoat layer 5 of the transparent resin layer 4, and the topcoat layer 5 is formed in the recessed part of the embossed pattern 4a by wiping. It is formed so that a part of the resin composition is embedded. The adhesive layer 7 is made of, for example, a heat sensitive adhesive, an anchor coat, a dry lamination adhesive, or the like. Moreover, the decorative sheet is formed by adhering the decorative sheet 1 to the base material B. The base material B is a wood board, an inorganic board, a metal plate, or the like.

[Topcoat layer 5]
The top coat layer 5 is formed by adding an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle to a resin composition that plays a role in protecting the surface and adjusting gloss.
Moreover, as a resin composition which is the main component of the topcoat layer 5, for example, polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, etc. It can be selected and used. The form of the resin composition is not particularly limited, such as aqueous, emulsion, solvent type. As for the curing method, a one-component type, a two-component type, an ultraviolet curing method or the like can be appropriately selected and used. In particular, urethane resins using isocyanate as the resin composition are suitable from the viewpoints of workability, cost, cohesive strength of the resin itself, and the like.

Examples of the isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis (isocyanate methyl). It can be appropriately selected from curing agents such as adducts, burettes, and isocyanurates that are derivatives of cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), and the like. In consideration of weather resistance, it is preferable to use a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a linear molecular structure. In addition to this, in order to improve the surface hardness, it is preferable to use a resin curable with active energy rays such as ultraviolet rays and electron beams. These resins can be used in combination with each other. For example, by using a hybrid type of a thermosetting resin and a photocurable resin, surface hardness is improved, curing shrinkage is suppressed, and a transparent resin layer is used. It is possible to improve the adhesion.

In addition, in order to impart various functions to the topcoat layer 5, for example, functional additives such as antibacterial agents and fungicides can be optionally added. Furthermore, in order to improve the surface design, for example, alumina, silica, silicon nitride, silicon carbide, glass beads, or the like may be added to adjust the gloss. Further, when the top coat layer 5 is added with, for example, alumina, silica, silicon nitride, silicon carbide, glass beads or the like, the surface wear resistance can be improved.

[Transparent resin layer 4]
As the transparent resin layer 4, it is preferable to use an olefin resin as a main component. Specific examples of the transparent resin layer 4 include, in addition to polypropylene, polyethylene, polybutene, and the like, α-olefins (for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene). 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene Or the like, or ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / vinyl methacrylate copolymer, Copolymerized ethylene or α-olefin with other monomers such as butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer Is mentioned. Moreover, when improving the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

In the decorative sheet 1 of the present embodiment, it is more preferable to add an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle to the transparent resin layer 4, respectively. Thereby, it becomes possible to provide weather resistance also in the transparent resin layer 4, and it can suppress that the olefin resin composition which is a main component of the transparent resin layer 4 deteriorates, or the pattern of the ink layer 3 located in the lower layer. Printing can be prevented from fading by ultraviolet rays, and excellent design can be maintained over a long period of time.

In addition to this, various additions such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjusting agent are added to the transparent resin layer 4 as necessary. An agent may be added. As a heat stabilizer, for example, phenol, sulfur, phosphorus, hydrazine, etc., as an ultraviolet absorber, for example, benzotriazole, benzoate, benzophenone, triazine, etc., as a light stabilizer, For example, hindered amines and the like are generally added in any combination.

[Adhesive layer 7]
The adhesive layer 7 is not particularly limited, and can be appropriately selected from, for example, acrylic, polyester, polyurethane, and epoxy. The coating method can be appropriately selected according to the viscosity of the adhesive and the like. In general, a gravure coat is used, and after applying the gravure coat to the upper surface of the ink layer 3, the transparent resin layer 4 And is to be laminated. The adhesive layer 7 can be omitted when the adhesive strength between the transparent resin layer 4 and the ink layer 3 is sufficiently obtained.

[Ink layer 3]
The ink layer 3 is a pattern print formed on the raw fabric layer 2 using ink. For example, nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester as a binder It can be used by selecting it appropriately from single or each modified product of the system. These may be water-based, solvent-based, or emulsion-type, and may be one-component type or two-component type using a curing agent. Furthermore, you may use the method of hardening ink by irradiation of an ultraviolet-ray, an electron beam, etc. Among them, the most common method is to use urethane-based ink and is a method of curing with isocyanate. In addition to these binders, colorants such as pigments and dyes contained in ordinary inks, extender pigments, solvents, various additives, and the like are added. Examples of highly versatile pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica. In addition to the ink application, the design can be applied by vapor deposition or sputtering of various metals.

Further, in the decorative sheet 1 of the present embodiment, it is preferable that a light stabilizer is added to the ink layer 3. By adding a light stabilizer to the ink layer 3, it is possible to prevent the ink from being photodegraded to impair the design properties, and to maintain the excellent design properties of the decorative sheet 1 over a long period of time.

[Original fabric layer 2]
As the raw fabric layer 2, for example, paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and the like are synthesized. Resin or foam of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer It can be arbitrarily selected from polymer rubber, rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, metal foil such as aluminum, iron, gold and silver.
When it is desired to impart concealability to the decorative sheet 1, concealment is imparted by making the original fabric layer 2 a colored sheet, or the original fabric layer 2 remains a transparent sheet, and an opaque concealment layer 8 is separately provided. It can be provided to provide concealment.

[Hidden layer 8]
The hiding layer 8 can be basically composed of the same material as the ink layer 3. Since the masking layer 8 is intended to provide masking properties, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide or the like as the pigment. Moreover, in order to improve the concealing property, for example, a metal such as gold, silver, copper, and aluminum can be added. In general, flaky aluminum is often added.

Further, when an olefin resin is used as the raw fabric layer 2, the surface thereof is often inactive. Therefore, it is preferable to provide the primer layer 6 between the raw fabric layer 2 and the base material B. In addition to this, in order to improve the adhesion between the raw material layer 2 made of an olefin-based material and the base material B, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, It is desirable to perform ultraviolet treatment, dichromic acid treatment or the like.

[Primer layer 6]
As the primer layer 6, basically, the same material as that of the ink layer 3 described above can be used. Considering that the primer layer 6 is applied to the back surface of the decorative sheet 1 and taking up in a web shape, in order to avoid blocking and increase adhesion with the adhesive, for example, silica, alumina, An inorganic filler such as magnesia, titanium oxide, or barium sulfate may be added to the primer layer 6.

[Formation of decorative sheet 1]
In forming the decorative sheet 1 of the present embodiment, the laminating method is not particularly limited, and is formed by appropriately selecting from commonly used methods such as a method using hot pressure, an extrusion laminating method, and a dry laminating method. can do. In the case of forming the embossed pattern 4a, a method is used in which the embossed pattern 4a is laminated by the above laminating method and then the embossed pattern 4a is put by hot pressure, or a concavo-convex pattern is provided on the cooling roll and the embossed pattern 4a is formed simultaneously with extrusion lamination. be able to.

In the decorative sheet 1 of this embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability and cost, the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the topcoat layer. 5 is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 400 μm.

<Effect of this embodiment>
In such a decorative sheet 1 of the present embodiment, the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle are added to at least one of the top coat layer 5 and the transparent resin layer 4, which is high. While maintaining transparency and having excellent design properties, it is possible to achieve excellent weather resistance over a long period of time.

Moreover, in the decorative sheet 1 of this embodiment, since the organic ultraviolet absorber vesicle and the inorganic ultraviolet absorber vesicle are used, high dispersibility with respect to the resin composition as the main component is realized, and the ultraviolet absorber Without increasing the addition amount, high UV absorption performance can be expressed and excellent weather resistance can be realized. Furthermore, since there is no bleeding out or white turbidity of the resin composition due to the agglomerated additive in the resin composition, there is no stickiness on the sheet surface, and the makeup has excellent adhesion and design. The sheet 1 can be provided. In particular, by making the both vesicles into vesicles having an outer membrane made of phospholipid, the compatibility with the resin composition which is the main component of the topcoat layer 5 and the transparent resin layer 4 is extremely good. Can do.

In addition, in the decorative sheet 1 of the present embodiment, the top coat layer 5 is embedded in the concave portion of the embossed pattern 4a, so that high weather resistance is maintained even in the concave portion where the layer thickness is thin. can do.
Moreover, since the fading of the ink layer 3 due to ultraviolet rays can be suppressed by forming the ink layer 3 using ink added with a light stabilizer, a design that retains beautiful color pattern printing over a long period of time. A decorative sheet 1 having excellent properties can be provided.

Hereinafter, the effect of this embodiment will be described in more detail.
(1) The decorative sheet 1 of the present embodiment is a decorative sheet provided with a top coat layer 5 on the outermost layer and a transparent resin layer 4 on the lower layer of the top coat layer 5, and the top coat layer 5 and the transparent resin layer 4. At least one of the organic ultraviolet absorber and the inorganic ultraviolet absorber is added to the vesicle having the outer layer of the single-layer film. The organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle are separately included.

With such a configuration, for at least one of the topcoat layer 5 and the transparent resin layer 4, both an organic ultraviolet absorber vesicle excellent in transparency and an inorganic ultraviolet absorber vesicle excellent in weather resistance are provided. Since it is added, it is possible to provide a decorative sheet capable of realizing both excellent design properties and long-term weather resistance. In addition, organic UV absorber vesicles and inorganic UV absorber vesicles are added separately in the form of vesicles, so the amount of both UV absorber vesicles added depending on the function to be added to the product Can be easily changed. More specifically, when transparency is important, the addition amount of the organic ultraviolet absorbent vesicle is increased by decreasing the addition amount of the inorganic ultraviolet absorbent vesicle. In order to prolong the service life, the addition amount of the organic ultraviolet absorbent vesicle is decreased by decreasing the addition amount of the organic ultraviolet absorbent vesicle.

(2) In the decorative sheet 1 of the present embodiment, the outer membrane of the vesicle may be formed of phospholipid.
With such a configuration, the compatibility with the resin composition that is the main component of the topcoat layer 5 and the transparent resin layer 4 can be improved, and thus high dispersibility of vesicles in the resin composition It is possible to suppress the occurrence of secondary aggregation.

(3) In the decorative sheet 1 of the present embodiment, the organic ultraviolet absorber may be benzotriazole, triazine, benzophenone, benzoate, or cyanoacrylate.
Such a configuration makes it possible to provide a decorative sheet that maintains high transparency and is excellent in design.

(4) In the decorative sheet 1 of the present embodiment, the inorganic ultraviolet absorber may be zinc oxide.
With such a configuration, it is possible to provide a decorative sheet excellent in functionality while maintaining ultraviolet absorbing ability over a long period of time.

(5) In the decorative sheet 1 of the present embodiment, the embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the topcoat layer 5 side, and the topcoat layer 5 is embedded in the recess of the embossed pattern 4a. It may be provided.
With such a configuration, the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle are also formed in the concave portion of the embossed pattern 4a in which the film thickness of the transparent resin layer 4 is reduced by forming the embossed pattern 4a. Since the added topcoat layer 5 is embedded, it is possible to provide a decorative sheet that provides weather resistance comparable to other parts.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.
<Preparation of organic UV absorber vesicles and inorganic UV absorber vesicles>
Hereinafter, a detailed method for preparing an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle using the supercritical reverse phase evaporation method in this embodiment will be described. A supercritical reverse phase evaporation method was used for the preparation of the vesicle.

The vesicles were prepared by using 100 parts by weight of hexane and a triazine-based UV absorber 2- (4,6-bis (2,4-dimethyl) as an organic UV absorber for a high-pressure stainless steel container kept at 60 ° C. Phenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl as a main component hydroxyphenyltriazine (TINUVIN 400; manufactured by BASF) 70 parts by weight or zinc oxide as an inorganic ultraviolet absorber ( 70 parts by weight (average particle size 20 nm) and 5 parts by weight of phosphatidylcholine as phospholipid are sealed, carbon dioxide is injected so that the pressure in the container becomes 20 MPa, and the mixture is vigorously stirred and mixed. While injecting 100 parts by weight of ethyl acetate, stirring and mixing for 15 minutes while maintaining the temperature and pressure, the carbon dioxide was discharged and the atmosphere It was returned to the. Thus, an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle having a single-layer outer membrane made of phospholipid was obtained.

<Examples 1-1 to 1-5>
In Examples 1-1 to 1-5, the organic ultraviolet absorbent vesicles 0.5 and 1 prepared by the above-described method were applied to the urethane resin as the resin composition that is the main component of the topcoat layer 5. 0.0, 5.0, 10.0, 20.0 parts by weight and inorganic ultraviolet absorbent vesicles 0.5, 1.0, 5.0, 10.0, 20 prepared by the above method. A decorative sheet 1 to which 0.0 part by weight was added was obtained.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin added with 0.2 part by weight was melt extruded using an extruder to form a transparent high crystalline polypropylene sheet having a thickness of 80 μm as the transparent resin layer 4. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). The topcoat layer 5 was formed by applying vesicles and inorganic ultraviolet absorber vesicles added in the combinations shown in Table 1 respectively. Thus, decorative sheets 1 of Examples 1-1 to 1-5 having a total thickness of 160 μm were obtained.

<Examples 1-6 to 1-10>
In Examples 1-6 to 1-10, the organic ultraviolet absorbent vesicle 0.1 prepared by the above-described method was used for the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. , 0.5, 1.0, 2.5, 5.0 parts by weight, and inorganic ultraviolet absorbent vesicles 0.1, 0.5, 1.0, 2.5 prepared by the above-described method The decorative sheet 1 was added with 5.0 parts by weight.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. Thickness as a transparent resin layer 4 is obtained by melt-extruding 0.2 parts by weight of a resin in which an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle are added in combinations of Table 2 using an extruder. A transparent high crystalline polypropylene sheet having a thickness of 80 μm was formed. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, and then a two-component urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ) is applied to the topcoat layer 5 Formed. Thus, decorative sheets 1 of Examples 1-6 to 1-10 having a total thickness of 160 μm were obtained.

<Example 1-11>
In Example 1-11, 1.25 parts by weight of the organic ultraviolet absorbent vesicle prepared by the above-described method was added to the urethane-based resin as the resin composition that is the main component of the topcoat layer 5, In addition to adding 1.25 parts by weight of the inorganic ultraviolet absorber vesicle prepared by the method, the organic homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4 was prepared by the above-described method. The decorative sheet 1 was obtained by adding 1.25 parts by weight of a UV absorber vesicle and 1.25 parts by weight of an inorganic UV absorber vesicle prepared by the above method.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. A resin to which 0.2 part by weight, 1.25 parts by weight of an organic ultraviolet absorbent vesicle and 1.25 parts by weight of an inorganic ultraviolet absorbent vesicle were added was melt-extruded using an extruder, and the transparent resin layer 4 As a film, a transparent highly crystalline polypropylene sheet having a thickness of 80 μm was formed. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the primer layer 6, the adhesive layer 7, and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). A top coat layer 5 was formed by applying 1.25 parts by weight of a vesicle and 1.25 parts by weight of an inorganic ultraviolet absorber vesicle. Thus, a decorative sheet 1 of Example 1-11 having a total thickness of 160 μm was obtained.

<Comparative Examples 1-1 and 1-2>
In Comparative Examples 1-1 and 1-2, 0.5 or 50.0 wt% of an organic ultraviolet absorber that is not vesicles is used with respect to the urethane resin as the resin composition that is the main component of the topcoat layer 5. And a decorative sheet 1 to which 0.5 or 50.0 parts by weight of an inorganic ultraviolet absorber that was not vesicles was added. Other configurations are the same as those of the decorative sheets 1 of Examples 1-1 to 1-5.

<Comparative Examples 1-3, 1-4>
In Comparative Examples 1-3 and 1-4, the non-vesicular organic ultraviolet absorber 0.5 or 50. A decorative sheet 1 was prepared by adding 0 part by weight and adding 0.5 or 50.0 parts by weight of an inorganic ultraviolet absorber that was not vesicled. Other configurations are the same as those of the decorative sheet 1 of Examples 1-6 to 1-10.

<Comparative Example 1-5>
In Comparative Example 1-5, 0.5 part by weight of the non-vesicled organic ultraviolet absorber was added to the urethane-based resin as the resin composition that is the main component of the topcoat layer 5, and the inorganic was not vesicled. In addition to adding 0.5 part by weight of the ultraviolet absorber, 0.5% of the organic ultraviolet absorber that is not vesicled is added to the crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4. The decorative sheet 1 was added with 0.5 parts by weight of an inorganic UV absorber that was not vesicled by weight. Other configurations are the same as those of the decorative sheet 1 of Example 1-11.

<Comparative Example 1-6>
In Comparative Example 1-6, the decorative sheet 1 was obtained in which no ultraviolet absorber was added to any resin layer. Other configurations are the same as those of the decorative sheet 1 of Example 1-1.

<Evaluation>
For each decorative sheet 1 of Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-6 obtained by the above method, a weather resistance tester (Sunshine Weather Meter: Suga Test Instruments Co., Ltd.) Carbon arc weather resistance test in accordance with JIS B 7753 was used to calculate the ultraviolet absorbing ability. The test conditions were as follows: weather resistance time of 4000 hours. As for the ultraviolet absorption ability, the ultraviolet absorption rate of the transparent layer composed of the top coat layer 5 and the transparent resin layer 4 of each decorative sheet 1 is measured, and the weather resistance of the ratio of ultraviolet absorption rate between 340 nm and 500 nm (340 nm / 500 nm). The difference between before and after the sex test is calculated. About the haze value, the value after a weather resistance test was measured. For the color difference (ΔE), the color difference (ΔE) of each decorative sheet 1 before and after the weather resistance test was calculated. Furthermore, the results of visual evaluation of the appearance change after the weather resistance test are indicated by the following symbols. The evaluation results obtained are shown in Table 1, Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2, and Examples 1-6 to 1-10 and Comparative Examples 1-3 and 1-4. Table 2 and Examples 1-11 and Comparative Examples 1-5 and 1-6 are shown in Table 3, respectively.

<Appearance change symbol>
◎: No change ○: Slight change △: Slight whitening and cracks ×: Severe whitening and partial destruction / breakage

First, the case where an ultraviolet absorber is added to the top coat layer 5 will be described. As shown in Table 1, the evaluation results are as follows: 0.5 to 20.0 parts by weight of the organic ultraviolet absorbent vesicle and 0.5 to 20.0 parts by weight of the inorganic ultraviolet absorbent vesicle with respect to the topcoat layer 5 With respect to the decorative sheets 1 of Examples 1-1 to 1-5 added, the value of the ultraviolet absorbing ability is small regardless of the amount added, and even after the 4000 hour weather resistance test, it is almost the same as before the test. It can be seen that it has no UV absorption performance. In addition, since the haze value after the test is small and the color difference (ΔE) value before and after the weather resistance test is also small, it has high transparency even after the weather resistance evaluation for 4000 hours, and almost no color change appears. I understand that. In the visual evaluation, excellent evaluation results were obtained. On the other hand, the decorative sheet 1 of Comparative Example 1-1 in which 0.5 parts by weight of the organic UV absorber and the inorganic UV absorber that were not vesicled with respect to the top coat layer 5 was added was UV absorbing. The performance value is 1.54, the haze value is 17.20%, and the color difference (ΔE) value is 7.43, showing a large value. The UV absorption rate decreased during the 4000 hour weather resistance test. It can be seen that the transparent layer deteriorates and the transparency is impaired. Also in the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because organic UV absorbers and inorganic UV absorbers that are not vesicles are used, resulting in poor dispersibility with respect to the resin composition as the main component, resulting in secondary aggregation, and sufficient UV absorption performance. It is thought that the cause was not. For the decorative sheet of Comparative Example 1-2 in which 50.0 parts by weight of an organic ultraviolet absorber and an inorganic ultraviolet absorber that are not vesicled are added to the topcoat layer 5, the value of the ultraviolet absorbing ability is Although it was as small as 0.01, the haze value was very large at 21.79% due to the addition of a large amount of ultraviolet absorber, and severe whitening was observed in visual evaluation. This is considered to be caused by the occurrence of blocking due to excessive addition of both UV absorbers and white turbidity.

Next, the case where an ultraviolet absorber is added to the transparent resin layer 4 will be described. As shown in Table 2, the results are shown in Table 2. Addition of 0.1 to 5.0 parts by weight of the organic ultraviolet absorbent vesicle and 0.1 to 5.0 parts by weight of the inorganic ultraviolet absorbent vesicle to the transparent resin layer 4 With respect to the decorative sheets 1 of Examples 1-6 to 1-10, the value of the ultraviolet absorbing ability was extremely small regardless of the amount added, and even after the 4000-hour weather resistance test, it was almost the same as before the test. It can be seen that it has no UV absorption rate. In addition, since the haze value after the test is small and the color difference (ΔE) value before and after the weather resistance test is also small, it has high transparency even after the weather resistance evaluation for 4000 hours, and almost no color change appears. I understand that. In the visual evaluation, excellent evaluation results were obtained. On the other hand, for the decorative sheet 1 of Comparative Example 1-3 in which 0.5 parts by weight of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent that are not vesicled are added to the transparent resin layer 4, the ultraviolet absorbent is used. The performance value is 1.32, the haze value is 16.30%, and the color difference (ΔE) value is 6.21, showing a large value, and the UV absorption rate decreased during the 4000-hour weather resistance test. It can be seen that the transparent layer deteriorates and the transparency is impaired. Also in the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because organic UV absorbers and inorganic UV absorbers that are not vesicles are used, resulting in poor dispersibility with respect to the resin composition as the main component, resulting in secondary aggregation, and sufficient UV absorption performance. It is thought that the cause was not. Further, for the decorative sheet of Comparative Example 1-4 in which 50.0 parts by weight of an organic ultraviolet absorber and an inorganic ultraviolet absorber that are not vesicled are added to the transparent resin layer 4, the value of the ultraviolet absorbing ability is Although it was as small as 0.01, the haze value was very large at 26.75% due to the addition of a large amount of an ultraviolet absorber, and severe whitening was observed in visual evaluation. It is considered that this is because the amount of both UV absorbers added was too large and bleedout occurred and the solution became cloudy.

Then, the case where an ultraviolet absorber is added to both the top coat layer 5 and the transparent resin layer 4 will be described. As shown in Table 3, the evaluation results are as shown in Example 1-11 in which 1.25 parts by weight of an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle were added to the topcoat layer 5 and the transparent resin layer 4. The decorative sheet 1 has a very small value of 0.09, a UV absorption value of 0.09, a haze value of 7.22%, and a color difference (ΔE) value of 0.25, and the weather resistance test for 4000 hours. It can be seen that the decorative sheet 1 has excellent ultraviolet absorption performance and high design with excellent transparency. On the other hand, with respect to the decorative sheet 1 of Comparative Example 1-5 in which 0.5 parts by weight of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent that are not vesicled are added to the topcoat layer 5 and the transparent resin layer 4. Shows a large value in all of the values of ultraviolet absorbing ability, haze value and color difference (ΔE), and is inferior in ultraviolet absorbing performance and designability as compared with the decorative sheet 1 of Example 1-11. I understand that. This is because the use of an ultraviolet absorber that was not vesicles resulted in inferior dispersibility in the resin composition as the main component, resulting in secondary agglomeration and failure to exhibit sufficient ultraviolet absorption performance. Conceivable.

Further, for the decorative sheet 1 of Comparative Example 1-6 in which no ultraviolet absorber was added to any of the resin layers, the ultraviolet absorption value was 10.80, the haze value was 6.47%, and the color difference ( The value of ΔE) was 12.20. From the results of visual evaluation, it can be seen that remarkable whitening and cracks occur after the weather resistance test, and that the weather resistance is poor.

Also, the decorative sheets 1 of Example 1-3 and Example 1-11 are compared as follows. The decorative sheet 1 of Example 1-3 to which 5.0 parts by weight of both UV absorber vesicles are added to the top coat layer 5, and 1.25 parts by weight to the top coat layer 5 and the transparent resin layer 4 respectively. In comparison with the decorative sheet 1 of Example 1-11 to which both UV absorber vesicles were added, the decorative sheet 1 of Example 1-11 was superior in all evaluation results, and only the top coat layer 5 was used. Even if a large amount of ultraviolet absorber vesicle is not added, a cosmetic sheet 1 having better ultraviolet absorption performance can be obtained by adding the ultraviolet absorber vesicle to the top coat layer 5 and the transparent resin layer 4 little by little. I understand that.

From the above evaluation results, as shown in the decorative sheets 1 of Examples 1-1 to 1-5, 0.5 to 20.0 parts by weight of the organic ultraviolet absorbent vesicle and inorganic with respect to the topcoat layer 5 are obtained. It was revealed that the decorative sheet 1 having excellent weather resistance and designability can be obtained over a long period of time by adding the ultraviolet absorber vesicle.

Further, as shown in the decorative sheet 1 of Examples 1-6 to 1-10, 0.1 to 5.0 parts by weight of the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent are used with respect to the transparent resin layer 4. It has been clarified that by adding the agent vesicle, the decorative sheet 1 having excellent weather resistance and designability can be obtained over a long period of time.

Further, as shown in the decorative sheet 1 of Example 1-11, an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle are added to both the topcoat layer 5 and the transparent resin layer 4. Thus, it has been clarified that the decorative sheet 1 having excellent ultraviolet absorption performance can be obtained without adding a large amount of ultraviolet absorber to either the top coat layer 5 or the transparent resin layer 4.

[Reference example]
Hereinafter, a decorative sheet other than the decorative sheet described in the present embodiment will be briefly described as a reference example of the present invention.
In recent years, many decorative sheets using olefinic resins have been proposed as decorative sheets replacing vinyl chloride decorative sheets. In addition, in order to improve the scratch resistance of a flexible polyolefin sheet made of an olefin resin generally used as a decorative sheet, there is a problem that the use of a resin having high crystallinity and high isotacticity results in poor weather resistance. It was.

As a technique for improving the weather resistance of a polyolefin-based resin, as disclosed in Patent Document 1, it is disclosed that a topcoat layer made of a resin containing a triazine-based organic ultraviolet absorber is provided on the surface of a polyolefin sheet. ing.
However, when a triazine-based UV absorber, which is an organic UV absorber, is added, the transparency of the base resin can be maintained, but the change over time is unavoidable, and there is a problem with the sustainability of UV absorption performance over a long period of time. Had.

In addition, when zinc oxide, which is an inorganic UV absorber, is added, the UV absorption performance over a long period is good with little change over time, but when added in a large amount, the transparency decreases and the decorative sheet itself has a good design. There was a problem of losing.
Furthermore, in both organic and inorganic ultraviolet absorbers, if the amount added is increased to improve the weather resistance, the ultraviolet absorber aggregates in the resin and bleed out occurs, causing stickiness on the sheet surface. There was a problem of causing a decrease in adhesion.
In addition to this, when an embossed pattern is formed on the transparent resin layer in order to improve the design of the decorative sheet, the concave portion of the embossed pattern is thinner than other parts, so that the layer thickness is thinner, so that the weather resistance Is particularly low, and there is a problem in that deterioration starts from the concave portion and whitening or breakage occurs.

As a result of intensive studies, the present inventors have used organic UV absorbers and inorganic UV absorbers vesicled by the supercritical reverse phase evaporation method, respectively. It was found that excellent weather resistance can be obtained.
Note that the supercritical reverse phase evaporation method is disclosed in Japanese Patent Application Publication Nos. 2002/032564, 2003-119120, 2005-298407, and 2008-063274 proposed by the present inventors. This is disclosed in a gazette (hereinafter referred to as “supercritical reverse phase evaporation method publications”), and was performed using the method and apparatus described in the supercritical reverse phase evaporation method publications.

(Second Embodiment)
The decorative sheet of the present embodiment is a decorative sheet provided with a top coat layer on the outermost layer and a transparent resin layer made of a transparent olefin resin under the top coat layer, the top coat layer and the transparent resin layer. At least one of these is added with an organic ultraviolet absorber and an inorganic ultraviolet absorber.

In the decorative sheet of the present embodiment, the organic and inorganic ultraviolet absorbers in which the organic ultraviolet absorber and the inorganic ultraviolet absorber are encapsulated together in a vesicle having a single-layer outer membrane. It is important to be a drug vesicle. Since extremely high dispersibility can be realized in the resin composition which is the main component of at least one of the topcoat layer and the transparent resin layer, at least one of the topcoat layer and the transparent resin layer having better ultraviolet absorption performance Can be provided.

When the organic ultraviolet absorber and the inorganic ultraviolet absorber are added to the topcoat layer, the organic ultraviolet absorber is 0 with respect to 100 parts by weight of the resin composition as the main component of the topcoat layer. It is preferable to add an organic / inorganic ultraviolet absorbent vesicle prepared so that the inorganic ultraviolet absorbent is in the range of 0.5 to 20 parts by weight and 0.5 to 20 parts by weight. At this time, if the addition amount of both ultraviolet absorbers is less than 0.5 parts by weight, the effect of ultraviolet absorbing ability is low, and if it is more than 20 parts by weight, the possibility of blocking increases. More preferably, the organic ultraviolet absorber is 1 to 10 parts by weight and the inorganic ultraviolet absorber is 1 to 10 parts by weight with respect to 100 parts by weight of the resin composition as the main component of the topcoat layer. Organic / inorganic ultraviolet absorber vesicles prepared so as to be added, more preferably 3 to 5 parts by weight of organic ultraviolet absorber, and 3 parts by weight of inorganic ultraviolet absorber An organic / inorganic ultraviolet absorber vesicle prepared to be in the range of ˜5 parts by weight is added.

Further, when added to the transparent resin layer, the organic ultraviolet absorber vesicle is 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin composition which is the main component of the transparent resin layer. It is preferable to add an organic / inorganic ultraviolet absorber vesicle prepared such that the ultraviolet absorber vesicle is in the range of 0.1 to 5 parts by weight. At this time, if the addition amount of both UV absorbers is less than 0.1 parts by weight, the effect of UV absorbing ability is low, and if it is more than 5 parts by weight, the possibility of bleeding out increases. More preferably, the organic ultraviolet absorber is 0.2 to 3 parts by weight and the inorganic ultraviolet absorber is 0.2 parts by weight to 100 parts by weight of the resin composition that is the main component of the transparent resin layer. An organic / inorganic ultraviolet absorber vesicle prepared so as to be in the range of 3 parts by weight is added.

Also, in the decorative sheet of the present embodiment, it is important that an embossed pattern is formed in the transparent resin layer, and a topcoat layer is embedded at least in the concave portion of the embossed pattern. More preferably, it is preferable to form the top coat layer in the recess by wiping.

Also, it is important that an ink layer formed of an ink to which at least a light stabilizer is added is provided under the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, it is possible to suppress the fading of the pigment due to the radicals generated by the resin degradation of the ink layer binder resin itself and other layers reducing the chemical components of the pigment in the ink. .

In addition, about the organic type ultraviolet absorber and inorganic type ultraviolet absorber used in this embodiment, since the same thing as 1st Embodiment can be used, description is abbreviate | omitted here.
Further, the organic / inorganic ultraviolet absorbent vesicle used in the present embodiment is prepared by the same supercritical reverse phase evaporation method as in the first embodiment. Therefore, the description about the preparation method of an organic type / inorganic type ultraviolet absorber vesicle is omitted here.
In addition, the phospholipid forming the outer membrane of the vesicle and the other substances forming the outer membrane of the vesicle used in the present embodiment can be the same as those in the first embodiment, and thus the description thereof is omitted here. .

Hereinafter, a specific configuration of the decorative sheet of the present embodiment will be described with reference to FIG.
(overall structure)
FIG. 1 shows a specific configuration of the decorative sheet 1 of the present embodiment, and the decorative sheet 1 is composed of a plurality of resin layers. In the decorative sheet 1 of this embodiment, a top coat layer 5, a transparent resin layer 4, an adhesive layer 7, an ink layer 3, an original fabric layer 2, a concealing layer 8 and a primer layer 6 are laminated from the surface layer side. Moreover, in order to improve designability, the embossed pattern 4a is formed in the surface at the side of the topcoat layer 5 of the transparent resin layer 4, and the topcoat layer 5 is formed in the recessed part of the embossed pattern 4a by wiping. It is formed so that a part of the resin composition is embedded. The adhesive layer 7 is made of, for example, a heat sensitive adhesive, an anchor coat, a dry lamination adhesive, or the like. Moreover, the decorative sheet is formed by adhering the decorative sheet 1 to the base material B. The base material B is a wood board, an inorganic board, a metal plate, or the like.

That is, the configuration of the decorative sheet 1 of the present embodiment is the same as the configuration of the decorative sheet 1 of the first embodiment described above. In addition, about the resin composition etc. which comprise each said layer, the resin composition etc. substantially the same as each layer demonstrated in 1st Embodiment can be used. Therefore, description of the same resin composition and the like as in the first embodiment is omitted here.
The top coat layer 5 is formed by adding an organic / inorganic ultraviolet absorbent vesicle to a resin composition that plays a role of protecting the surface and adjusting gloss.

In the decorative sheet 1 of the present invention, it is more preferable to add an organic / inorganic ultraviolet absorbent vesicle to the transparent resin layer 4. Thereby, it becomes possible to provide weather resistance also in the transparent resin layer 4, and it can suppress that the olefin resin composition which is a main component of the transparent resin layer 4 deteriorates, or the pattern of the ink layer 3 located in the lower layer. Printing can be prevented from fading by ultraviolet rays, and excellent design can be maintained over a long period of time.

In the decorative sheet 1 of the present embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability and cost, the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the top. The coat layer 5 is desirably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 400 μm.

<Effect of this embodiment>
In the decorative sheet 1 of the present embodiment, the organic / inorganic ultraviolet absorber vesicle is added to at least one of the topcoat layer 5 and the transparent resin layer 4, and thus excellent transparency is maintained. In addition to having design properties, it is possible to achieve excellent weather resistance over a long period of time.

Further, in the decorative sheet 1 of the present embodiment, since organic and inorganic ultraviolet absorbent vesicles that encapsulate both ultraviolet absorbents are used, extremely high dispersibility with respect to the resin composition as the main component. Therefore, it is possible to realize excellent weather resistance by expressing high ultraviolet absorption performance without increasing the amount of the ultraviolet absorber added. Furthermore, since there is no bleeding out or white turbidity of the resin composition due to the agglomerated additive in the resin composition, there is no stickiness on the sheet surface, and the makeup has excellent adhesion and design. The sheet 1 can be provided. In particular, by using the vesicle as a vesicle having an outer membrane made of phospholipid, the compatibility with the resin composition which is the main component of the topcoat layer 5 and the transparent resin layer 4 is extremely good. it can.

In addition, in the decorative sheet 1 of the present embodiment, the top coat layer 5 is embedded in the concave portion of the embossed pattern 4a, so that high weather resistance is maintained even in the concave portion where the layer thickness is thin. can do.
Moreover, since the fading of the ink layer 3 due to ultraviolet rays can be suppressed by forming the ink layer 3 using ink to which a light stabilizer is added, a design that maintains beautiful color printing for a long period of time. A decorative sheet 1 having excellent properties can be provided.

Hereinafter, the effect of this embodiment will be described in more detail.
(1) The decorative sheet 1 of the present embodiment is a decorative sheet that includes a top coat layer 5 in the outermost layer and a transparent resin layer 4 in the lower layer of the top coat layer 5, and includes the top coat layer and the transparent resin layer 4. At least one contains an organic UV absorber and an inorganic UV absorber, and the organic UV absorber and the inorganic UV absorber are contained together in a vesicle having a single-layer outer membrane. It is characterized by being an organic / inorganic ultraviolet absorber vesicle.
With such a configuration, both an organic ultraviolet absorber excellent in transparency and an inorganic ultraviolet absorber excellent in weather resistance are added to at least one of the top coat layer 5 and the transparent resin layer 4. Therefore, it is possible to provide a decorative sheet capable of realizing both excellent design properties and long-term weather resistance. Moreover, in the resin composition which is the main component of at least one of the topcoat layer and the transparent resin layer by using an organic / inorganic ultraviolet absorber vesicle in which both ultraviolet absorbers are encapsulated together in one vesicle. Since extremely high dispersibility can be realized, it is possible to provide a decorative sheet having more excellent ultraviolet absorption performance.

(2) In the decorative sheet 1 of the present embodiment, the outer membrane of the vesicle may be formed of phospholipid.
With such a configuration, the compatibility with the resin composition that is the main component of the topcoat layer 5 and the transparent resin layer 4 can be improved, and thus high dispersibility of vesicles in the resin composition It is possible to suppress the occurrence of secondary aggregation.

(3) In the decorative sheet 1 of the present embodiment, the organic ultraviolet absorber may be benzotriazole, triazine, benzophenone, benzoate, or cyanoacrylate.
Such a configuration makes it possible to provide a decorative sheet that maintains high transparency and is excellent in design.

(4) In the decorative sheet 1 of the present embodiment, the inorganic ultraviolet absorber may be zinc oxide.
Such a configuration makes it possible to provide a decorative sheet that maintains high transparency and is excellent in design.

(5) In the decorative sheet 1 of the present embodiment, the embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the topcoat layer 5 side, and the topcoat layer 5 is embedded in the recess of the embossed pattern 4a. It may be provided.
If it is such a structure, the top which the organic and inorganic type ultraviolet absorber vesicle was added also in the recessed part of the embossed pattern 4a in which the film thickness of the transparent resin layer 4 is thin by forming the embossed pattern 4a Since the coat layer 5 is embedded, it is possible to provide a decorative sheet that provides weather resistance comparable to other parts.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.
<Preparation of organic and inorganic UV absorber vesicles>
Hereinafter, a detailed method for preparing an organic / inorganic ultraviolet absorbent vesicle using the supercritical reverse phase evaporation method in the present embodiment will be described. A supercritical reverse phase evaporation method was used for the preparation of the vesicle.

The vesicles were prepared by using 100 parts by weight of hexane and a triazine-based UV absorber 2- (4,6-bis (2,4-dimethyl) as an organic UV absorber for a high-pressure stainless steel container kept at 60 ° C. Phenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl as a main component, 35 parts by weight of hydroxyphenyltriazine (TINUVIN 400; manufactured by BASF) and zinc oxide as an inorganic ultraviolet absorber ( 35 parts by weight (average particle size 20 nm) and 5 parts by weight of phosphatidylcholine as phospholipid are put in a sealed state, carbon dioxide is injected so that the pressure in the container becomes 20 MPa, and the mixture is brought into a supercritical state, and vigorously stirred and mixed. While injecting 100 parts by weight of ethyl acetate, stirring and mixing for 15 minutes while maintaining the temperature and pressure, the carbon dioxide was discharged. It was returned to the pressure. Thus, a vesicled organic / inorganic ultraviolet absorbent vesicle having an outer membrane of phospholipid was obtained.

<Examples 2-1 to 2-5>
In Examples 2-1 to 2-5, the organic and inorganic ultraviolet absorbent vesicles 1. The decorative sheet 1 was added with 07, 2.13, 10.66, 21.32, and 42.64 parts by weight. The ratio of the added organic / inorganic ultraviolet absorbent vesicle is 0.5, 1.0, 5.0, 10.0, 20.0 parts by weight for the organic ultraviolet absorbent, The absorbent was 0.5, 1.0, 5.0, 10.0, 20.0 parts by weight.

Specifically, 0.05 parts by weight of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine-based light stabilizer (Kimasorb 944; BASF) with respect to the highly crystalline homopolypropylene resin. The resin to which 0.2 part by weight of the product was added was melt extruded using an extruder to form a transparent highly crystalline polypropylene sheet having a thickness of 80 μm as the transparent resin layer 4. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) on one surface of a polyethylene sheet (raw fabric layer 2) having a concealing property as the raw fabric layer 2 Pattern printing was performed to provide a 3 μm ink layer 3, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry lamination as an adhesive layer 7 having a transparent resin layer 4 formed to a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, and then an organic / inorganic system is applied to a two-component urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). The top coat layer 5 was formed by applying the ultraviolet absorbent vesicles added in the combinations shown in Table 4 respectively. Thus, decorative sheets 1 of Examples 2-1 to 2-5 having a total thickness of 160 μm were obtained.

<Examples 2-6 to 2-10>
In Examples 2-6 to 2-10, the organic / inorganic ultraviolet absorbent vesicle prepared by the above-described method was used for the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. It was set as the decorative sheet 1 which added 0.21, 1.07, 2.13, 5.33, 10.66 weight part. The ratio of the added organic / inorganic ultraviolet absorber vesicle is 0.1, 0.5, 1.0, 2.5, 5.0 parts by weight for the organic ultraviolet absorber, The absorbent was 0.1, 0.5, 1.0, 2.5, 5.0 parts by weight.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. Resin added with 0.2 part by weight of organic / inorganic ultraviolet absorber vesicles in combination shown in Table 5 was melt-extruded using an extruder to form transparent resin layer 4 having a thickness of 80 μm. A highly crystalline polypropylene sheet was formed. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, and then a two-component urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ) is applied to the topcoat layer 5 Formed. Thus, decorative sheets 1 of Examples 2-6 to 2-10 having a total thickness of 160 μm were obtained.

<Example 2-11>
In Example 2-11, 2.67 parts by weight of the organic / inorganic ultraviolet absorbent vesicle prepared by the above-described method was added to the urethane resin as the resin composition which is the main component of the topcoat layer 5. In addition to the addition of 2.67 parts by weight of the organic / inorganic ultraviolet absorbent vesicle prepared by the above-mentioned method to the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4 A decorative sheet 1 was obtained. The organic / inorganic ultraviolet absorbent vesicle added to the top coat layer 5 was 1.25 parts by weight of the organic ultraviolet absorbent and 1.25 parts by weight of the inorganic ultraviolet absorbent. . The ratio of the organic / inorganic ultraviolet absorbent vesicle added to the transparent resin layer 4 was 1.25 parts by weight of the organic ultraviolet absorbent and 1.25 parts by weight of the inorganic ultraviolet absorbent. .

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. A transparent high crystal having a thickness of 80 μm as the transparent resin layer 4 is obtained by melting and extruding 0.2 part by weight of a resin to which 2.67 parts by weight of an organic / inorganic ultraviolet absorber vesicle is added using an extruder. A conductive polypropylene sheet was formed. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, and then an organic / inorganic system is applied to a two-component urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). A topcoat layer 5 was formed by applying a material to which 2.67 parts by weight of an ultraviolet absorber vesicle was added. Thus, a decorative sheet 1 of Example 2-11 having a total thickness of 160 μm was obtained.

<Comparative Examples 2-1 and 2-2>
In Comparative Examples 2-1 and 2-2, 0.5 or 50.0% by weight of an organic ultraviolet absorber that is not vesicled with respect to the urethane resin as the resin composition that is the main component of the topcoat layer 5 The decorative sheet 1 was added with 0.5 part or 50.0 parts by weight of an inorganic ultraviolet absorber that was not vesicled. Other configurations are the same as those of the decorative sheet 1 of Examples 2-1 to 2-5.

<Comparative Examples 2-3 and 2-4>
In Comparative Examples 2-3 and 2-4, an organic ultraviolet absorber 0.5 or 50. not vesicle is used with respect to the crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. A decorative sheet 1 was prepared by adding 0 part by weight and adding 0.5 or 50.0 parts by weight of an inorganic ultraviolet absorber that was not vesicled. Other configurations are the same as those of the decorative sheet 1 of Examples 2-6 to 2-10.

<Comparative Example 2-5>
In Comparative Example 2-5, 0.5 part by weight of non-vesicled organic UV absorber, non-vesicled inorganic based on urethane resin as the resin composition that is the main component of topcoat layer 5 In addition to adding 0.5 part by weight of the ultraviolet absorber, 0.5% of the organic ultraviolet absorber that is not vesicled is added to the crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4. The decorative sheet 1 was added with 0.5 parts by weight of an inorganic UV absorber that was not vesicled by weight. Other configurations are the same as those of the decorative sheet 1 of Example 2-11.

<Comparative Example 2-6>
In Comparative Example 2-6, the decorative sheet 1 was obtained in which no ultraviolet absorber was added to any resin layer. Other configurations are the same as those of the decorative sheet 1 of Example 2-1.

<Evaluation>
For each decorative sheet 1 of Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-6 obtained by the above method, the ultraviolet absorptivity and haze value were obtained in the same manner as in the first embodiment. The color change (ΔE) and the appearance change after the weather resistance test were evaluated. The obtained evaluation results are shown in Table 4 for Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2, and in Examples 2-6 to 2-10 and Comparative Examples 2-3 and 2-4. Table 5 shows Examples 5-11 and Comparative Examples 2-5 and 2-6, respectively. Note that the meaning of the sign of appearance change is the same as in the first embodiment.

First, the case where an ultraviolet absorber is added to the top coat layer 5 will be described. As shown in Table 4, the results of Examples 2-1 to 2-5 in which 1.07 to 42.64 parts by weight of an organic / inorganic ultraviolet absorber vesicle were added to the topcoat layer 5 were obtained. It can be seen that the sheet 1 has a UV absorption performance that is small in the value of the UV absorption ability and has almost the same as that before the test even after the 4000-hour weather resistance test, regardless of the addition amount. In addition, since the haze value after the test is small and the color difference (ΔE) value before and after the weather resistance test is also small, it has high transparency even after the weather resistance evaluation for 4000 hours, and almost no color change appears. I understand that. In the visual evaluation, excellent evaluation results were obtained. On the other hand, with respect to the decorative sheet 1 of Comparative Example 2-1, in which 0.5 parts by weight of each of the organic UV absorber and the inorganic UV absorber which are not vesicles are added to the topcoat layer 5, the UV absorption The performance value is 1.54, the haze value is 17.20%, and the color difference (ΔE) value is 7.43, showing a large value. The UV absorption rate decreased during the 4000 hour weather resistance test. It can be seen that the transparent layer deteriorates and the transparency is impaired. Also in the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because organic UV absorbers and inorganic UV absorbers that are not vesicles are used, resulting in poor dispersibility with respect to the resin composition as the main component, resulting in secondary aggregation, and sufficient UV absorption performance. It is thought that the cause was not. For the decorative sheet of Comparative Example 2-2 in which 50.0 parts by weight of the organic UV absorber and the inorganic UV absorber that were not vesicled were added to the topcoat layer 5, the value of the UV absorbing ability was Although it was as small as 0.01, the haze value was very large at 21.79% due to the addition of a large amount of ultraviolet absorber, and severe whitening was observed in visual evaluation. This is considered to be caused by the occurrence of blocking due to excessive addition of both UV absorbers and white turbidity.

Next, the case where an ultraviolet absorber is added to the transparent resin layer 4 will be described. The evaluation results are as shown in Table 5. The decorative sheets of Examples 2-6 to 2-10 in which 0.21 to 10.66 parts by weight of organic / inorganic ultraviolet absorber vesicles were added to the transparent resin layer 4 It can be seen that No. 1 has an ultraviolet absorptivity that is extremely small even after the weather resistance test for 4000 hours, which is almost the same as that before the test, regardless of the amount added. In addition, since the haze value after the test is small and the color difference (ΔE) value before and after the weather resistance test is also small, it has high transparency even after the weather resistance evaluation for 4000 hours, and almost no color change appears. I understand that. In the visual evaluation, excellent evaluation results were obtained. On the other hand, the decorative sheet 1 of Comparative Example 2-3, in which 0.5 parts by weight of each of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent that are not vesicled with respect to the transparent resin layer 4 was added, was UV absorbent. The performance value is 1.32, the haze value is 16.30%, and the color difference (ΔE) value is 6.21, showing a large value, and the UV absorption rate decreased during the 4000-hour weather resistance test. It can be seen that the transparent layer deteriorates and the transparency is impaired. Also in the visual evaluation, whitening and cracks were observed after the weather resistance test. This is because organic UV absorbers and inorganic UV absorbers that are not vesicles are used, resulting in poor dispersibility with respect to the resin composition as the main component, resulting in secondary aggregation, and sufficient UV absorption performance. It is thought that the cause was not. Further, for the decorative sheet of Comparative Example 2-4 in which 50.0 parts by weight of an organic ultraviolet absorber and an inorganic ultraviolet absorber that are not vesicled are added to the transparent resin layer 4, the value of the ultraviolet absorbing ability is Although it was as small as 0.01, the haze value was very large at 26.75% due to the addition of a large amount of an ultraviolet absorber, and severe whitening was observed in visual evaluation. It is considered that this is because the amount of both UV absorbers added was too large and bleedout occurred and the solution became cloudy.

Then, the case where an ultraviolet absorber is added to both the top coat layer 5 and the transparent resin layer 4 will be described. The evaluation results are as shown in Table 6. The decorative sheet 1 of Example 2-11 was obtained by adding 2.67 parts by weight of organic and inorganic ultraviolet absorbent vesicles to the topcoat layer 5 and the transparent resin layer 4 respectively. The UV absorption value is 0.07, the haze value is 5.88%, and the color difference (ΔE) value is 0.37, showing extremely small values. A 4000 hour weather resistance test was conducted. It can be seen that this is a decorative sheet 1 that has excellent ultraviolet absorption performance and excellent design properties with high transparency. On the other hand, the decorative sheet 1 of Comparative Example 2-5, in which 0.5 parts by weight of an organic ultraviolet absorbent and an inorganic ultraviolet absorbent that were not vesicled with respect to the top coat layer 5 and the transparent resin layer 4 were added, respectively. As for the UV absorption ability value, haze value and color difference (ΔE), all the values are large, and inferior in UV absorption performance and designability compared to the decorative sheet 1 of Example 2-11. I understand that. This is because the use of an ultraviolet absorber that was not vesicles resulted in inferior dispersibility in the resin composition as the main component, resulting in secondary agglomeration and failure to exhibit sufficient ultraviolet absorption performance. Conceivable.

Further, for the decorative sheet 1 of Comparative Example 2-6 in which no ultraviolet absorber was added to any of the resin layers, the ultraviolet absorptivity value was 10.80, the haze value was 6.47%, and the color difference ( The value of ΔE) was 12.20. From the results of visual evaluation, it can be seen that remarkable whitening and cracks occur after the weather resistance test, and that the weather resistance is poor.

Also, the decorative sheets 1 of Example 2-3 and Example 2-11 are compared as follows. The decorative sheet 1 of Example 2-3 to which 10.66 parts by weight of an organic / inorganic ultraviolet absorber vesicle was added to the top coat layer 5, and 2 to the top coat layer 5 and the transparent resin layer 4 respectively. When compared with the decorative sheet 1 of Example 2-11 to which .67 parts by weight of an organic / inorganic ultraviolet absorber vesicle was added, the decorative sheet 1 of Example 2-11 was superior in all evaluation results. Even if a large amount of UV absorber vesicles are not added only to the top coat layer 5, it is possible to improve UV absorption performance by adding UV absorber vesicles to the top coat layer 5 and the transparent resin layer 4 little by little. It can be seen that the decorative sheet 1 having the above is obtained.

From the above evaluation results, as shown in the decorative sheet 1 of Examples 2-1 to 2-5, 1.07 to 42.64 parts by weight of organic and inorganic ultraviolet absorbers with respect to the topcoat layer 5 It became clear that the decorative sheet 1 excellent in weather resistance and designability can be obtained over a long period of time by adding vesicles. Here, of the organic and inorganic ultraviolet absorbent vesicles added to the top coat layer 5, the organic ultraviolet absorbent is 0.5 to 20.0 parts by weight, and the inorganic ultraviolet absorbent is 0.5 to 20. 0 parts by weight.

Further, as shown in the decorative sheet 1 of Examples 2-6 to 2-10, 0.21 to 10.66 parts by weight of an organic / inorganic ultraviolet absorbent vesicle is added to the transparent resin layer 4. As a result, it was clarified that the decorative sheet 1 having excellent weather resistance and designability can be obtained over a long period of time. Here, of the organic and inorganic ultraviolet absorbent vesicles added to the transparent resin layer 4, the organic ultraviolet absorbent is 0.1 to 5.0 parts by weight, and the inorganic ultraviolet absorbent is 0.1 to 5. 0 parts by weight.

Further, as shown in the decorative sheet 1 of Example 2-11, by adding an organic / inorganic ultraviolet absorbent vesicle to both the top coat layer 5 and the transparent resin layer 4, the top It has been clarified that the decorative sheet 1 having excellent ultraviolet absorption performance can be obtained without adding a large amount of ultraviolet absorber to either the coat layer 5 or the transparent resin layer 4.

(Third embodiment)
The decorative sheet of the present embodiment is a decorative sheet provided with a top coat layer on the outermost layer and a transparent resin layer made of a transparent olefin resin under the top coat layer, the top coat layer and the transparent resin layer. Any one of these resin layers contains an organic ultraviolet absorber and an inorganic ultraviolet absorber.
Then, either one of the organic ultraviolet absorbent or the inorganic ultraviolet absorbent is an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle enclosed in a vesicle having a single-layer outer membrane. It is important that

Further, in the decorative sheet according to the first modified example of the present embodiment, in addition to the configuration of the above embodiment, the other resin layer not selected in the above embodiment has an organic ultraviolet absorber or an inorganic ultraviolet absorber. The organic ultraviolet absorbent or the inorganic ultraviolet absorbent is an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle encapsulated in a vesicle having a single-layer outer membrane. Yes.

Further, in the decorative sheet according to the second modified example of the present embodiment, in addition to the configuration of the above embodiment, the other resin layer not selected in the above embodiment includes an organic ultraviolet absorber and an inorganic ultraviolet absorber. An organic UV absorber vesicle or an inorganic UV absorber in which one of the organic UV absorber and the inorganic UV absorber is included in a vesicle having a single-layer outer film It is considered a vesicle.

The organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle in the above-described embodiment and its modifications are the organic ultraviolet absorbent or the inorganic ultraviolet ray in a vesicle-like capsule having a membrane structure closed in a spherical shell shape. It has a structure in which an absorbent is included. The organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle have extremely high dispersibility without causing the particles to aggregate due to the action of the outer films repelling each other.

For this reason, in the resin composition constituting at least one of the top coat layer and the transparent resin layer of the decorative sheet of this embodiment and its modification, the dispersion of the organic ultraviolet absorbent vesicle or the inorganic ultraviolet absorbent vesicle is dispersed. The force prevents the inorganic ultraviolet absorbent or the organic ultraviolet absorbent that has not been vesicled from agglomerating, and both ultraviolet absorbents exist in a very uniformly dispersed state.

And as a result of realizing the high dispersibility of both UV absorbers in the resin composition, the top coat has excellent transparency that prevents the resin composition from becoming clouded due to the aggregated UV absorbers At least one of the layer and the transparent resin layer can be realized.
Furthermore, bleed-out such as bloom (powder spray) or bleed (liquid spray) generated when the agglomerated UV absorbers are ejected onto the surface of the resin composition does not occur. As a result, the content of both UV absorbers present in the resin composition does not decrease due to leakage of both UV absorbers, so that the topcoat layer and the transparent resin have excellent weather resistance over a long period of time. At least one of the layers can be realized.

In addition, one surface of the topcoat layer, which is the outermost surface of the decorative sheet and directly touches human skin during use, does not cause whitening due to bloom or stickiness due to bleed, etc. A feeling can be maintained. And on the other surface of the topcoat layer, which is the surface to be bonded to the other resin layer, and both surfaces of the transparent resin layer, no bloom or bleed is generated, thereby providing excellent adhesion between the resin layers over a long period of time. Can be realized.

Examples of a method for obtaining the organic ultraviolet absorbent vesicle or the inorganic ultraviolet absorbent vesicle of the present embodiment (vesicle forming method) include, for example, the Bangham method, the extrusion method, the hydration method, the reverse phase evaporation method, and the freeze-thaw method. And supercritical reverse phase evaporation. Briefly explaining such a vesicle treatment method, in the Bangham method, chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further dissolved therein. Thereafter, the solvent is removed using an evaporator to form a thin film composed of lipid, and after adding an additive dispersion, the mixture is hydrated and dispersed by a vortex mixer to obtain a vesicle. The extrusion method is a method of preparing a vesicle by preparing a thin phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method. The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining vesicles by gently stirring and dispersing without using a mixer. In the reverse phase evaporation method, phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to make a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added. This is a method for obtaining vesicles. The freeze-thaw method is a method using cooling / heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling / heating.

In particular, as a method for obtaining an ultraviolet absorbent vesicle having an outer film made of a single layer film, a supercritical reverse phase evaporation method can be mentioned. The supercritical reverse phase evaporation method is disclosed in JP-T-2002 / 032564, JP-A-2003-119120, JP-A-2005-298407, and JP-A-2008-063274 (provided by the present inventors). (Hereinafter referred to as “supercritical reverse phase evaporation method publications”), and can be carried out using the method and apparatus described in the supercritical reverse phase evaporation method publications.
Hereinafter, the organic ultraviolet absorbent vesicle or the inorganic ultraviolet absorbent vesicle composed of a substance containing a biological lipid such as phospholipid is referred to as an organic ultraviolet absorbent liposome or an inorganic ultraviolet absorbent liposome.

Here, you may make it form the outer membrane of the above-mentioned liposome from the mixture of a phospholipid and a dispersing agent. In the decorative sheet of this embodiment, the ultraviolet absorbent vesicle is preferably an ultraviolet absorbent liposome having an outer membrane made of phospholipid, and the outer membrane is made of phospholipid so that the topcoat layer and the transparent The compatibility between the resin material, which is the main component of the resin layer, and the vesicle can be improved.
In the present embodiment, the above-mentioned organic ultraviolet absorbent vesicle and inorganic ultraviolet absorbent vesicle are preferably added in the following proportions relative to at least one of the topcoat layer and the transparent resin layer. .

The ratio of addition will be described in detail. When added to the topcoat layer, 0.5 part by weight of the organic ultraviolet absorber vesicle is added to 100 parts by weight of the resin composition as the main component of the topcoat layer. It is preferable to add up to 20 parts by weight of an inorganic ultraviolet absorber vesicle in a proportion of 0.5 to 20 parts by weight. At this time, if the ratio of both ultraviolet absorbers is less than 0.5 parts by weight, the effect of ultraviolet absorbing ability is low, and if it is more than 20 parts by weight, the possibility of blocking increases. More preferably, 1 to 10 parts by weight of the organic ultraviolet absorber vesicle and 1 to 10 parts by weight of the inorganic ultraviolet absorber vesicle are added, and still more preferably, the organic ultraviolet absorber is absorbed. The additive vesicle is added in an amount of 3 to 5 parts by weight, and the inorganic ultraviolet absorber vesicle is added in an amount of 3 to 5 parts by weight.

In addition, when added to the transparent resin layer, 0.1 to 5 parts by weight of an organic ultraviolet absorbent vesicle is added to 100 parts by weight of the resin composition that is the main component of the transparent resin layer. The ultraviolet absorber vesicle is preferably added at a ratio of 0.1 to 5 parts by weight. At this time, if the ratio of both ultraviolet absorbers is less than 0.1 parts by weight, the effect of ultraviolet absorbing ability is low, and if it is more than 5 parts by weight, the possibility of bleeding out increases. More preferably, the organic ultraviolet absorbent vesicle is added in an amount of 0.2 to 3 parts by weight, and the inorganic ultraviolet absorbent vesicle is added in an amount of 0.2 to 3 parts by weight.

In addition, the addition amount of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent in the resin composition constituting at least one of the topcoat layer and the transparent resin layer may be different from each other. For example, by further reducing the amount of the organic ultraviolet absorber added and increasing the amount of the inorganic ultraviolet absorber added, it is possible to further extend the ultraviolet absorbing performance. On the contrary, by increasing the amount of organic UV absorber added and decreasing the amount of inorganic UV absorber added, the transparency of the topcoat layer and the transparent resin layer can be improved. Designability can be realized.

Further, while adding both ultraviolet absorbers in the above ratio to either the topcoat layer or the transparent resin layer, the organic ultraviolet absorber vesicle or the inorganic ultraviolet ray is added to the other resin layer. When the absorber vesicle is added, the ratio of both UV absorber vesicles is 0.5 to 20 parts by weight with respect to 100 parts by weight of the resin composition as the main component of the topcoat layer. It is preferably added at a ratio of 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin composition as the main component of the transparent resin layer.

Furthermore, it is important that an ink layer containing at least a light stabilizer is provided under the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, the binder resin itself that forms the ink layer and radicals generated by resin degradation of the other layer reduce the chemical component of the pigment in the ink, thereby fading the pigment. It can suppress and can hold a colorful picture over a long period of time.

In addition, about the organic type ultraviolet absorber and inorganic type ultraviolet absorber used in this embodiment, since the same thing as 1st Embodiment can be used, description is abbreviate | omitted here.
In addition, the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent vesicle used in the present embodiment are prepared by the same supercritical reverse phase evaporation method as in the first embodiment. Therefore, the description about the preparation method of an organic type ultraviolet absorber vesicle and an inorganic type ultraviolet absorber vesicle is abbreviate | omitted here.
In addition, the phospholipid forming the outer membrane of the vesicle and the other substances forming the outer membrane of the vesicle used in the present embodiment can be the same as those in the first embodiment, and thus the description thereof is omitted here. .

Hereinafter, a specific configuration of the decorative sheet of the present embodiment will be described with reference to FIG.
Specific embodiments of the above-described embodiment and its modifications are listed in the following (1) to (10).
(1) The top coat layer contains both ultraviolet absorbers, and the organic ultraviolet absorber is a vesicle.
(2) The top coat layer contains both UV absorbers, and the inorganic UV absorber is a vesicle.
(3) The transparent resin layer contains both ultraviolet absorbers, and the organic ultraviolet absorber is a vesicle.
(4) The transparent resin layer contains both UV absorbers, and the inorganic UV absorber is a vesicle.
(5) In addition to the constitution of (1) or (2), the transparent resin layer contains an organic ultraviolet absorber vesicle.
(6) In addition to the constitution of (1) or (2), the transparent resin layer contains an inorganic ultraviolet absorbent vesicle.
(7) In addition to the constitution of (3) or (4), the top coat layer contains an organic ultraviolet absorber vesicle.
(8) In addition to the constitution of (3) or (4), the top coat layer contains an inorganic ultraviolet absorbent vesicle.
(9) In addition to the configuration of (1) or (2), the configuration of (3) is adopted.
(10) In addition to the configuration of (1) or (2), the configuration of (4) is adopted.

(overall structure)
FIG. 1 shows a specific configuration of the decorative sheet 1 of the present embodiment, and is a configuration combining the above (1) and (3).

The decorative sheet 1 of this embodiment is composed of a plurality of resin layers. In the decorative sheet 1 of this embodiment, a top coat layer 5, a transparent resin layer 4, an adhesive layer 7, an ink layer 3, an original fabric layer 2, a concealing layer 8 and a primer layer 6 are laminated from the surface layer side. Moreover, in order to improve designability, the embossed pattern 4a is formed in the surface at the side of the topcoat layer 5 of the transparent resin layer 4, and the topcoat layer 5 is formed in the recessed part of the embossed pattern 4a by wiping. It is formed so that a part of the resin composition is embedded. In particular, in the decorative sheet 1 of the present embodiment, the top coat layer 5 and the transparent resin layer 4 are composed of a resin composition containing an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent. The adhesive layer 7 is made of, for example, a heat sensitive adhesive, an anchor coat, a dry lamination adhesive, or the like. Moreover, the decorative sheet is formed by adhering the decorative sheet 1 to the base material B.
That is, the configuration of the decorative sheet 1 of the present embodiment is the same as the configuration of the decorative sheet 1 of the first embodiment described above. In addition, about the resin composition etc. which comprise each said layer, the resin composition etc. substantially the same as each layer demonstrated in 1st Embodiment can be used. Therefore, description of the same resin composition and the like as in the first embodiment is omitted here.

The topcoat layer 5 is made of a resin composition that plays a role of protecting the surface and adjusting gloss, and the resin composition contains an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent.
Moreover, in the transparent resin layer 4 in the decorative sheet 1 of the present embodiment, the resin composition contains an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent in order to further impart ultraviolet absorption performance. By using the resin composition containing the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent, the deterioration of the main component olefin resin material can be suppressed, or the pattern of the ink layer 3 located in the lower layer can be suppressed. Printing can be prevented from fading by ultraviolet rays, and excellent design can be maintained over a long period of time.

In the decorative sheet 1 of the present embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability and cost, the ink layer 3 is 5 μm to 20 μm, the adhesive layer 7 is 1 μm to 20 μm, and a transparent resin. The layer 4 is desirably 20 μm to 200 μm, the topcoat layer 5 is desirably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 49 μm to 410 μm.

<Effect of this embodiment>
In the decorative sheet 1 of the present embodiment, the top coat layer 5 and the transparent resin layer 4 are composed of a resin composition containing an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent, so that excellent transparency and A decorative sheet having high UV absorption performance can be realized.

Specifically, since the organic ultraviolet absorber is added as a vesicle, the dispersibility of the organic ultraviolet absorber vesicle is included in the resin composition constituting the top coat layer 5 and the transparent resin layer 4. Therefore, not only the organic ultraviolet absorber but also the inorganic ultraviolet absorber can be present in a uniformly dispersed state without agglomeration. As a result, light scattering due to the aggregated ultraviolet absorber is suppressed, and high transparency is realized.

Furthermore, in the resin composition, since both ultraviolet absorbers are uniformly dispersed, bleed out such as bloom (powder spray) or bleed (liquid spray) due to the aggregated ultraviolet absorber does not occur. .
Further, by making the ink layer 3 to which a light stabilizer is added, it is possible to suppress fading of the ink layer 3 due to ultraviolet rays, and it is a decorative sheet excellent in design properties that retains beautiful color pattern printing over a long period of time. 1 can be provided.

Hereinafter, the effect of this embodiment will be described in more detail.
(1) The decorative sheet 1 of the present embodiment is a decorative sheet provided with a top coat layer 5 on the outermost layer and a transparent resin layer 4 on the lower layer of the top coat layer 5, and the top coat layer 5 and the transparent resin layer 4. Any one of the resin layers contains an organic ultraviolet absorber and an inorganic ultraviolet absorber, and any one of the organic ultraviolet absorber and the inorganic ultraviolet absorber contained in the resin layer is outside the single layer film. It is an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle encapsulated in a vesicle having a film.

(2) In the decorative sheet 1 of the present embodiment, the other resin layer not selected in the decorative sheet contains at least one of an organic ultraviolet absorbent or an inorganic ultraviolet absorbent, and contains ultraviolet rays. One of the absorbents may be an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle encapsulated in a vesicle having a single-layer outer membrane.

As described above, by making any one of the topcoat layer 5 and the transparent resin layer 4 into a resin layer containing an organic ultraviolet absorber and an inorganic ultraviolet absorber, it has excellent design properties, A decorative sheet capable of realizing excellent weather resistance over a long period of time can be provided.
And in the resin composition which comprises the topcoat layer 5 or the transparent resin layer 4 by containing either the organic type ultraviolet absorber and the inorganic type ultraviolet absorber to contain in the state made into the vesicle. The organic ultraviolet absorbent and the inorganic ultraviolet absorbent can be uniformly dispersed without aggregation.

Furthermore, as a result of realizing high dispersibility, bloom (powder spray) and bleed (liquid spray) generated due to the agglomerated organic UV absorber and inorganic UV absorber do not occur, and the decorative sheet The surface located on the outermost surface does not cause whitening or stickiness of the decorative sheet, and excellent adhesion to the other resin layer can be achieved on the surface that is bonded to the other resin layer.
Moreover, according to the decorative sheet 1 of the present embodiment, the other resin layer is a resin layer containing at least one of an organic ultraviolet absorber and an inorganic ultraviolet absorber, and one of the contained ultraviolet absorbers is a vesicle. By making it contain in the state made into the said, it becomes possible to provide the decorative sheet which was further excellent in weather resistance, without producing the said bloom (powder spray), a bleed (liquid spray), etc.

(3) In the decorative sheet 1 of the present embodiment, the outer membrane of the vesicle may be formed of phospholipid.
With such a configuration, the compatibility with the resin composition that is the main component of the topcoat layer 5 and the transparent resin layer 4 can be improved, and thus high dispersibility of vesicles in the resin composition It is possible to suppress the occurrence of secondary aggregation.

(4) In the decorative sheet 1 of the present embodiment, the organic ultraviolet absorber may be benzotriazole, triazine, benzophenone, benzoate, or cyanoacrylate.
Such a configuration makes it possible to provide a decorative sheet that maintains high transparency and is excellent in design.

(5) In the decorative sheet 1 of the present embodiment, the inorganic ultraviolet absorber may be zinc oxide.
With such a configuration, it is possible to provide a decorative sheet excellent in functionality while maintaining ultraviolet absorbing ability over a long period of time.

(6) In the decorative sheet 1 of the present embodiment, the embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the topcoat layer 5 side, and the topcoat layer 5 is embedded in the recess of the embossed pattern 4a. It may be provided.
With such a configuration, the organic ultraviolet absorbent vesicle or the inorganic ultraviolet absorbent vesicle is also formed in the concave portion of the embossed pattern 4a in which the film thickness of the transparent resin layer 4 is reduced by forming the embossed pattern 4a. Since the added top coat layer 5 is embedded, it is possible to provide a decorative sheet that provides weather resistance comparable to other parts.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.

<Preparation of organic UV absorber vesicles and inorganic UV absorber vesicles>
First, a detailed method for preparing an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle used in Examples 3-1 to 3-15 below will be described. A supercritical reverse phase evaporation method was used for the preparation of the vesicle.

The vesicles were prepared by using 100 parts by weight of hexane and a triazine-based UV absorber 2- (4,6-bis (2,4-dimethyl) as an organic UV absorber for a high-pressure stainless steel container kept at 60 ° C. Phenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl as a main component hydroxyphenyltriazine (TINUVIN 400; manufactured by BASF) 70 parts by weight or zinc oxide as an inorganic ultraviolet absorber ( 70 parts by weight (average particle size 20 nm) and 5 parts by weight of phosphatidylcholine as phospholipid are sealed, carbon dioxide is injected so that the pressure in the container becomes 20 MPa, and the mixture is vigorously stirred and mixed. Inject 100 parts by weight of ethyl acetate while stirring and mixing for 15 minutes while maintaining the temperature and pressure, and then discharge carbon dioxide into the atmosphere. It was returned to the. Thus, an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle having a single-layer outer membrane made of phospholipid was obtained.

<Example 3-1>
In Example 3-1, the decorative sheet 1 having the form (1) was examined. In Example 3-1, the organic ultraviolet absorbent vesicles 0.5, 1.0, 5.0, 10 and 10 are used with respect to 100 parts by weight of the urethane resin as the resin composition which is the main component of the top coat layer 5. 0.0, 20.0 and 50.0 parts by weight were added, and inorganic ultraviolet absorbers 0.5, 1.0, 5.0, 10.0, 20.0 and 0.5 parts by weight were added. A decorative sheet 1 was obtained.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin added with 0.2 part by weight was melt extruded using an extruder to form a transparent high crystalline polypropylene sheet having a thickness of 80 μm as the transparent resin layer 4. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). 0.5, 1.0, 5.0, 10.0, 20.0, 50.0 parts by weight of vesicle, 0.5, 1.0, 5.0, 10.0 of an inorganic ultraviolet absorber, The topcoat layer 5 was formed by applying the material added at a ratio of 20.0 and 0.5 parts by weight. Thus, a decorative sheet 1 of Example 3-1 having a total thickness of 160 μm was obtained.

<Example 3-2>
In Example 3-2, the decorative sheet 1 having the form (2) was examined. In Example 3-2, the organic ultraviolet absorbers 0.5, 1.0, 5.0, 10. While adding 0,20.0 weight part, it was set as the decorative sheet 1 which added the inorganic type ultraviolet absorber vesicle 0.5, 1.0, 5.0, 10.0, 20.0 weight part. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-1.

<Example 3-3>
In Example 3-3, the decorative sheet 1 having the form (3) was examined. In Example 3-3, with respect to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4, the organic ultraviolet absorbent vesicles 0.1, 0.5, 1 A decorative sheet 1 to which 0.0, 2.5, 5.0 parts by weight and 0.1, 0.5, 1.0, 2.5, 5.0 parts by weight of an inorganic ultraviolet absorber are added did.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. 0.2 parts by weight, organic ultraviolet absorber vesicle 0.1, 0.5, 1.0, 2.5, 5.0 parts by weight, inorganic ultraviolet absorber 0.1, 0.5, 1.0 The resin added at a ratio of 2.5, 5.0 parts by weight was melt extruded using an extruder to form a transparent highly crystalline polypropylene sheet having a thickness of 80 μm as the transparent resin layer 4. . The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, and then a two-component urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ) is applied to the topcoat layer 5 Formed. Thus, a decorative sheet 1 of Example 3-3 having a total thickness of 160 μm was obtained.

<Example 3-4>
In Example 3-4, the decorative sheet 1 having the form (4) was examined. In Example 3-4, the organic ultraviolet absorbers 0.1, 0.5, 1..., 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4 are used. 0, 2.5, 5.0, 0.5 parts by weight are added, and inorganic ultraviolet absorber vesicles 0.1, 0.5, 1.0, 2.5, 5.0, 20.0 weights are added. A decorative sheet 1 with parts added thereto was obtained. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-3.

<Example 3-5>
In Example 3-5, the decorative sheet 1 having the configuration adopting the form (2) in the form (5) was examined. In Example 3-5, 0.5 part by weight of the organic ultraviolet absorber is added to 100 parts by weight of the urethane resin as the resin composition that is the main component of the topcoat layer 5, and the inorganic ultraviolet ray is added. 0.5 part by weight of the absorbent vesicle is added, and 0.5 part by weight of the organic ultraviolet absorbent vesicle is added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. The decorative sheet 1 was added.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. A transparent high crystalline polypropylene sheet having a thickness of 80 μm as a transparent resin layer 4 is obtained by melting and extruding 0.2 parts by weight of a resin added with 0.5 parts by weight of an organic ultraviolet absorber vesicle using an extruder. Was formed. Thereafter, both surfaces of the formed highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry laminating as an adhesive layer 7 having a transparent resin layer 4 formed in a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. After the embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, the organic ultraviolet absorption is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). The top coat layer 5 was formed by applying 0.5 parts by weight of an agent and 0.5 parts by weight of an inorganic ultraviolet absorber vesicle. Thus, a decorative sheet 1 of Example 3-5 having a total thickness of 160 μm was obtained.

<Example 3-6>
In Example 3-6, the decorative sheet 1 having the configuration adopting the form (2) in the form (6) was examined. In Example 3-6, 0.5 part by weight of the organic ultraviolet absorber is added to 100 parts by weight of the urethane resin as the resin composition which is the main component of the topcoat layer 5, and the inorganic ultraviolet ray is added. 0.5 part by weight of the absorbent vesicle is added, and 0.5 part by weight of the inorganic ultraviolet absorbent vesicle is added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. The decorative sheet 1 was added. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-5.

<Example 3-7>
In Example 3-7, the decorative sheet 1 having the configuration adopting the form (4) in the form (7) was examined. In Example 3-7, 0.5 part by weight of an organic ultraviolet absorber vesicle was added to 100 parts by weight of the urethane resin as the resin composition that is the main component of the topcoat layer 5, and the transparent resin layer 4 parts by weight of an organic ultraviolet absorbent and 100 parts by weight of an inorganic ultraviolet absorbent vesicle with respect to 100 parts by weight of a highly crystalline homopolypropylene resin as a resin composition which is a main component of 4 The decorative sheet 1 was added.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. A resin added with 0.2 part by weight, 0.5 part by weight of an organic ultraviolet absorbent and 0.5 part by weight of an inorganic ultraviolet absorbent vesicle is melt-extruded using an extruder to form a transparent resin layer 4 A transparent highly crystalline polypropylene sheet having a thickness of 80 μm was formed. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry lamination as an adhesive layer 7 having a transparent resin layer 4 formed to a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). A topcoat layer 5 was formed by applying a vesicle added at a ratio of 0.5 part by weight. Thus, a decorative sheet 1 of Example 3-7 having a total thickness of 160 μm was obtained.

<Example 3-8>
In Example 3-8, the decorative sheet 1 having the configuration employing the form (4) in the form (8) described above was studied. In Example 3-8, 0.5 part by weight of the inorganic ultraviolet absorbent vesicle was added to 100 parts by weight of the urethane resin as the resin composition which is the main component of the topcoat layer 5, and the transparent resin layer 4 parts by weight of an organic ultraviolet absorbent and 100 parts by weight of an inorganic ultraviolet absorbent vesicle with respect to 100 parts by weight of a highly crystalline homopolypropylene resin as a resin composition which is a main component of 4 The decorative sheet 1 was added. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-7.

<Example 3-9>
In Example 3-9, the decorative sheet 1 having a configuration in which the form (1) and the form (3) in the form (9) described above were combined was examined. In Example 3-9, the organic ultraviolet absorber vesicles 0.5, 1.25, and 5.0 weights with respect to 100 parts by weight of the urethane resin as the resin composition that is the main component of the topcoat layer 5 100 parts by weight of a highly crystalline homopolypropylene resin as a resin composition that is a main component of the transparent resin layer 4. In addition to adding 0.5, 1.25 and 5.0 parts by weight of organic ultraviolet absorber vesicle, 0.5, 1.25 and 5.0 parts by weight of inorganic ultraviolet absorber were added. A decorative sheet 1 was obtained.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. Resin to which 0.2 parts by weight, 0.5, 1.25, 5.0 parts by weight of an organic ultraviolet absorbent vesicle and 0.5, 1.25, 5.0 parts by weight of an inorganic ultraviolet absorbent are added Then, it was melt-extruded using an extruder to form a transparent highly crystalline polypropylene sheet having a thickness of 80 μm as the transparent resin layer 4. The both surfaces of the thus obtained highly crystalline polypropylene sheet were subjected to corona treatment so that the wetting tension on the sheet surface was 40 dyn / cm or more. Next, pattern printing is performed on one surface of a 70 μm polyethylene sheet having a concealing property as the raw fabric layer 2 by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to 3 μm. Ink layer 3 was provided, and a primer coat was applied to the other surface of the polyethylene sheet as the original fabric layer 2 to form a 1 μm primer layer 6. Thereafter, an adhesive for dry lamination as an adhesive layer 7 having a transparent resin layer 4 formed to a thickness of 3 μm on the surface of the ink layer 3 formed on the polyethylene sheet (Takelac A540; manufactured by Mitsui Chemicals, Inc.) And bonded together by a dry laminating method. Thus, a laminated resin sheet having a thickness of 157 μm composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, the primer layer 6 and the transparent resin layer 4 was obtained. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of this laminated resin sheet, an organic ultraviolet absorber is applied to a two-pack type urethane topcoat (W184; manufactured by DIC Graphics, coating thickness 3 g / m ² ). The topcoat layer 5 was coated by applying 0.5, 1.25, 5.0 parts by weight of vesicle and 0.5, 1.25, 5.0 parts by weight of an inorganic ultraviolet absorber. Formed. Thus, a decorative sheet 1 of Example 3-9 having a total thickness of 160 μm was obtained.

<Example 3-10>
In Example 3-10, the decorative sheet 1 having a configuration in which the form (2) and the form (3) in the form (9) are combined was examined. In Example 3-10, 0.5 part by weight of the organic ultraviolet absorber is added to 100 parts by weight of the urethane resin as the resin composition that is the main component of the topcoat layer 5, and the inorganic ultraviolet ray is added. 0.5 part by weight of the absorbent vesicle is added, and 0.5 part by weight of the organic ultraviolet absorbent vesicle is added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. And a decorative sheet 1 to which 0.5 part by weight of an inorganic ultraviolet absorber was added. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-9.

<Example 3-11>
In Example 3-11, the decorative sheet 1 having a configuration combining the form (1) and the form (4) in the form (10) described above was studied. In Example 3-11, 0.5 part by weight of the organic ultraviolet absorbent vesicle is added to 100 parts by weight of the urethane resin as the resin composition that is the main component of the top coat layer 5, and the inorganic system 0.5 part by weight of the ultraviolet absorber is added, and 0.5 part by weight of the organic ultraviolet absorber is added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. While adding, it was set as the decorative sheet 1 which added 0.5 weight part of inorganic type ultraviolet absorber vesicles. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-9.

<Example 3-12>
In Example 3-12, the decorative sheet 1 having a configuration in which the form (2) and the form (4) in the form (10) are combined was examined. In Example 3-12, 0.5, 1.25, and 5.0 parts by weight of an organic ultraviolet absorber with respect to 100 parts by weight of the urethane resin as the resin composition that is the main component of the topcoat layer 5 100% by weight of a highly crystalline homopolypropylene resin as a resin composition that is a main component of the transparent resin layer 4 In addition to adding 0.5, 1.25 and 5.0 parts by weight of the organic ultraviolet absorber, 0.5, 1.25 and 5.0 parts by weight of the inorganic ultraviolet absorber vesicle were added. A decorative sheet 1 was obtained. Otherwise, the decorative sheet 1 was produced in the same configuration as in Example 3-9.

<Example 3-13>
In Example 3-13, in the decorative sheet 1 of the embodiments 3-1 to 3-4, 3-9, and 3-12, the hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) was used for the ink layer 3. ) Was added to the decorative sheet 1. The other configurations are the same as those in Examples 3-1 to 3-4, 3-9, and 3-12, and the ratios of both UV absorbers and both UV absorber vesicles are respectively shown in resin composition 100. The decorative sheet 1 was produced at 0.5 parts by weight with respect to parts by weight.

<Example 3-14>
Example 3-14 is a decorative sheet 1 having a configuration in which an organic ultraviolet absorber is added to the topcoat layer 5 as another resin layer in addition to the embodiment 3-4. Specifically, the organic ultraviolet absorber 0.5 part by weight is added to 100 parts by weight of the urethane resin as the resin composition which is the main component of the top coat layer 5, and the main component of the transparent resin layer 4 is added. A cosmetic composition in which 0.5 parts by weight of an organic ultraviolet absorbent and 0.5 parts by weight of an inorganic ultraviolet absorbent vesicle are added to 100 parts by weight of a highly crystalline homopolypropylene resin as a resin composition. Sheet 1 was obtained.

<Example 3-15>
In Example 3-15, in addition to the embodiment of Example 3-2, an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle were added to the transparent resin layer 4 as another resin layer. This is a decorative sheet 1. Specifically, an inorganic ultraviolet absorber vesicle is added to 0.5 parts by weight of an organic ultraviolet absorber with respect to 100 parts by weight of a urethane resin as a resin composition that is a main component of the topcoat layer 5. 0.5 part by weight is added, and 0.5 part by weight of the organic ultraviolet absorber vesicle is added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. In addition, a decorative sheet 1 to which 0.5 part by weight of an inorganic ultraviolet absorbent vesicle was added was obtained.

<Comparative Example 3-1>
In Comparative Example 3-1, 0.5 to 5.0 parts by weight of the organic ultraviolet absorber was added to 100 parts by weight of the urethane resin as the resin composition that is the main component of the topcoat layer 5, A decorative sheet to which 0.5 and 5.0 parts by weight of an inorganic ultraviolet absorber was added was obtained. Otherwise, a decorative sheet was produced in the same configuration as in Example 3-1.

<Comparative Example 3-2>
In Comparative Example 3-2, 0.5 to 1.0 part by weight of the organic ultraviolet absorber was added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition that is the main component of the transparent resin layer 4. While adding, it was set as the decorative sheet which added inorganic ultraviolet absorber 0.5 and 1.0 weight part. Otherwise, a decorative sheet was produced in the same configuration as in Example 3-3.

<Comparative Example 3-3>
In Comparative Example 3-3, 0.5 part by weight of the organic ultraviolet absorber is added to 100 parts by weight of the urethane resin as the resin composition which is the main component of the topcoat layer 5, and the inorganic ultraviolet absorber is absorbed. 0.5 parts by weight of the organic ultraviolet absorber is added to 100 parts by weight of the highly crystalline homopolypropylene resin as the resin composition which is the main component of the transparent resin layer 4. In addition, a decorative sheet to which 0.5 parts by weight of an inorganic ultraviolet absorber was added was obtained. Otherwise, a decorative sheet was produced in the same configuration as in Example 3-9.

<Comparative Example 3-4>
In Comparative Example 3-4, a decorative sheet including the top coat layer 5 and the transparent resin layer 4 to which neither of the ultraviolet absorbers was added was obtained.

<Evaluation>
For each decorative sheet 1 of Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-4 obtained by the above method, the ultraviolet absorbing ability and haze value were the same as in the first embodiment. The color change (ΔE) and the appearance change after the weather resistance test were evaluated. The obtained evaluation results are shown in Table 7 for Examples 3-1 to 3-4, Table 8 for Examples 3-5 to 3-12, Table 9 for Examples 3-13 to 3-15, and Comparative Examples. Table 10 shows 3-1 to 3-4. Note that the meaning of the sign of appearance change is the same as in the first embodiment.

In Examples 3-1 to 3-4, the decorative sheet 1 of the third embodiment of the present invention was examined.

As shown in Table 7, the decorative sheet 1 in Example 3-1 has an ultraviolet absorbing ability regardless of the ratio of the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent to the topcoat layer 5. The haze value and color difference (ΔE) show small values, and it can be seen that the weather resistance and transparency are excellent. It can be seen from the visual appearance change after the weather resistance test that almost no change was observed before and after the weather resistance test. However, in the decorative sheet 1 to which the organic ultraviolet absorber vesicle is added in a proportion of 50.0 parts by weight and the inorganic ultraviolet absorber is added in a proportion of 0.5 parts by weight, the appearance change such as color and cracks is changed. However, no bleed was observed on the surface. This is considered to have occurred because the amount of the organic ultraviolet absorber vesicle added was excessive.

As shown in Table 7, the decorative sheet 1 in Example 3-2 has an ultraviolet absorbing ability, regardless of the ratio of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent vesicle added to the top coat layer 5. The haze value and color difference (ΔE) show small values, and it can be seen that the weather resistance and transparency are excellent. In particular, the addition ratios of 5.0 and 10.0 parts by weight, respectively, show extremely small values in each test result, and also in the evaluation of visual changes after the weather resistance test. No change was observed compared to before the weather resistance test.

As shown in Table 7, the decorative sheet 1 in Example 3-3 has an ultraviolet absorbing ability, regardless of the ratio of the organic ultraviolet absorbent vesicle and the inorganic ultraviolet absorbent to the transparent resin layer 4. The haze value and color difference (ΔE) show small values, and little or no change is observed in the visual appearance change evaluation after the weather resistance test compared to before the weather resistance test. Thus, it can be seen that it has excellent weather resistance and transparency.

As shown in Table 7, the decorative sheet 1 in Example 3-4 has an ultraviolet absorbing ability, regardless of the ratio of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent vesicle added to the transparent resin layer 4. The haze value and color difference (ΔE) show extremely small values, and no change is observed in the visual appearance change evaluation after the weather resistance test as compared with before the weather resistance test. Excellent weather resistance and transparency It turns out that it is excellent in property. However, in the decorative sheet 1 to which an organic ultraviolet absorber is added at a ratio of 0.5 parts by weight and an inorganic ultraviolet absorber vesicle is added at a ratio of 20.0 parts by weight, the appearance change such as color and cracks is changed. Was not observed, but bloom (powder spray) was observed on the surface. This is considered to have occurred because the amount of the inorganic ultraviolet absorber vesicle added was excessive.

In these decorative sheets 1 in Examples 3-1 to 3-4, as compared with the decorative sheets in Comparative Examples 3-1 and 3-2 shown in Table 10, any one of the added ultraviolet absorbers is a vesicle. It can be seen that, even when the ratio is the same, the ultraviolet absorptivity, haze value, and color difference (ΔE) are small, and the weather resistance and transparency are excellent. This is because the dispersibility of both ultraviolet absorbers is improved by using an organic ultraviolet absorber vesicle or an inorganic ultraviolet absorber vesicle, and the ratio of the addition of both ultraviolet absorbers remaining in the resin composition It is thought that this is because white turbidity is suppressed by preventing aggregation of both ultraviolet absorbers while preventing the decrease in the amount of UV rays and exhibiting sufficient ultraviolet absorption performance.

Examples 3-5 to 3-8 were examined on the decorative sheet 1 according to the first modification of the third embodiment of the present invention.

As shown in Table 8, the decorative sheet 1 in Example 3-5 was applied to the transparent resin layer 4 in addition to the configuration of Example 3-2 in which both UV absorbers were added to the topcoat layer 5. By adding the organic ultraviolet absorber vesicle, the ultraviolet absorption capacity and the color difference (ΔE) were reduced, and the haze value was hardly changed. Also, in the visual appearance change evaluation after the weather resistance test, it was “◯” in Example 3-2, but “◎” in this example, and no change was observed. It was. From this result, in addition to the top coat layer 5 as one resin layer, by adding an organic ultraviolet absorber vesicle to the transparent resin layer 4 as another resin layer, the weather resistance is further improved. It became clear that it could be improved.

As shown in Table 8, the decorative sheet 1 in Example 3-6 has the same structure as that of Example 3-2 in which both UV absorbers are added to the top coat layer 5, but also the transparent resin layer 4. By adding the inorganic ultraviolet absorbent vesicle, the ultraviolet absorption ability and the color difference (ΔE) were decreased, and the haze value was slightly increased. Also, in the visual appearance change evaluation after the weather resistance test, it was “◯” in Example 3-2, but “◎” in this example, and no change was observed. It was. From this result, in addition to the top coat layer 5 as one resin layer, the transparency is slightly impaired by adding an inorganic ultraviolet absorber vesicle to the transparent resin layer 4 as the other resin layer. However, it was revealed that the decorative sheet 1 having extremely excellent weather resistance can be provided.

As shown in Table 8, the decorative sheet 1 in Example 3-7 has the same structure as that of Example 3-4 in which both UV absorbers are added to the transparent resin layer 4, but the top coat layer 5 has By adding the organic ultraviolet absorbent vesicle, the ultraviolet absorbing ability, haze value, and color difference (ΔE) were reduced. From this result, in addition to the transparent resin layer 4 as one resin layer, the organic UV absorber vesicle is added to the top coat layer 5 as the other resin layer, thereby providing extremely excellent weather resistance. It became clear that the decorative sheet 1 can be provided.

As shown in Table 8, the decorative sheet 1 in Example 3-8 includes the top coat layer 5 in addition to the configuration of Example 3-4 in which both UV absorbers are added to the transparent resin layer 4. By adding the inorganic ultraviolet absorbent vesicle, the value of the ultraviolet absorbing ability was decreased, and the haze value and the color difference (ΔE) were slightly increased. From this result, in addition to the transparent resin layer 4 as one resin layer, the transparency is slightly impaired by adding an inorganic ultraviolet absorber vesicle to the top coat layer 5 as the other resin layer. However, it was revealed that the decorative sheet 1 having extremely excellent weather resistance can be provided.

Examples 3-9 to 3-12 were examined on the decorative sheet 1 according to the second modification of the third embodiment of the present invention.

As shown in Table 8, the decorative sheet 1 in Examples 3-9 to 3-12 has an ultraviolet absorbing ability regardless of the ratio of both ultraviolet absorbers added to the top coat layer 5 and the transparent resin layer 4. , Haze value and color difference (ΔE) show small values, and even in the observation results of the appearance change after the weather resistance test, almost no change is observed, no change is observed, excellent weather resistance and transparency It turns out that it has sex.

In particular, in the decorative sheet 1 of Example 3-12 in which the inorganic ultraviolet absorber added to the top coat layer 5 and the transparent resin layer 4 are both vesicles, the ultraviolet absorptivity, haze value, and color difference (ΔE) The value was the smallest value, and it was revealed that it was extremely excellent in weather resistance and transparency as compared with the decorative sheet 1 in Examples 3-9 to 3-11. This is because in Example 3-12, since the inorganic ultraviolet absorber which is more easily aggregated is vesicled, the dispersibility of both ultraviolet absorbers in the resin composition is further improved, and the aggregated ultraviolet rays are absorbed. A large amount of both ultraviolet absorbers remain in the resin composition constituting the top coat layer 5 and the transparent resin layer 4 without causing bloom (powder spray) or bleed (liquid spray) due to the absorbent. This is considered to be superior in weather resistance as compared with the decorative sheet 1 in Examples 3-9 to 3-11. In addition, the vesicles of inorganic UV absorbers improve the dispersibility of both UV absorbers compared to vesicles of organic UV absorbers, suppress white turbidity, and have excellent haze. It is thought that the value was shown.

Further, the decorative sheets 1 in Examples 3-9 to 3-12 were compared with the test results of the decorative sheet of Comparative Example 3-3 shown in Table 10, and any of ultraviolet absorption ability, haze value, and color difference (ΔE) The results also show excellent results. By vesicleizing either one of the UV absorbers added to the top coat layer 5 and the transparent resin layer 4, the weather resistance is greatly improved, and excellent transparency. It can be seen that

Example 3-13 is a study in which the decorative sheet 1 of the third embodiment of the present invention and each modified example is further provided with an ink layer 3 to which a light stabilizer is added.

As shown in Table 9, the decorative sheet 1 in Example 3-13 has the same ratio of addition of both ultraviolet absorbers in the embodiments in Examples 3-1 to 3-4, 3-9, and 3-12. Even when compared with the sheet 1, the ultraviolet absorbing ability, haze value and color difference (ΔE) show slightly small values, and by making the decorative sheet 1 provided with the ink layer 3 to which a light stabilizer is added, From the decorative sheets 1 in the embodiments of Examples 3-1 to 3-4, 3-9, and 3-12, it was revealed that it was possible to achieve better weather resistance and transparency.

As shown in Table 9, the decorative sheet 1 in Example 3-14 was compared with the decorative sheet 1 having the structure of Example 3-4 with respect to the top coat layer 5 as the other resin layer. It has been clarified that by adding the absorbent, the decorative sheet 1 having a small ultraviolet absorption ability and color difference (ΔE) and having excellent weather resistance and transparency can be obtained. Further, compared with Example 3-7 in which an organic ultraviolet absorber vesicle was added to the topcoat layer 5 as the other resin layer, the haze value and the color difference (ΔE) were large. In the topcoat layer 5 in Example 3-14, it is considered that the organic ultraviolet absorber is aggregated.

As shown in Table 9, the decorative sheet 1 in Example 3-15 was compared with the decorative sheet 1 having the configuration of Example 3-2, with respect to the transparent resin layer 4 as the other resin layer, with organic ultraviolet rays. It has been clarified that the decorative sheet 1 having better weather resistance can be obtained by adding the absorbent vesicle and the inorganic ultraviolet absorbent vesicle.

As shown in Comparative Example 3-4, in the decorative sheet 1 having the top coat layer 5 and the transparent resin layer 4 to which neither UV absorber is added, the UV absorbing ability and the color difference (ΔE) show large values. From the observation result of the appearance change after the weather resistance test, it can be seen that it does not have weather resistance.

From the above results, in the decorative sheet 1 of the present embodiment, one of the top coat layer 5 and the transparent resin layer 4 contains an organic ultraviolet absorber and an inorganic ultraviolet absorber, and Since any one of the organic ultraviolet absorber and the inorganic ultraviolet absorber is contained in a vesicle, the decorative sheet 1 having excellent transparency and high ultraviolet absorption performance can be realized.

Further, by making the decorative sheet 1 to which at least one of an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle is added to the other resin layer, the decorative sheet 1 having further excellent transparency and ultraviolet absorbing performance. Can be realized.
And in addition to the above-mentioned configuration, by making the decorative sheet 1 provided with the ink layer 3 to which a light stabilizer is added, it is possible to maintain beautiful color print for a long period of time. Became clear.

[Reference example]
Hereinafter, a decorative sheet other than the decorative sheet described in the present embodiment will be briefly described as a reference example of the present invention.
The decorative sheet other than the decorative sheet described in the present embodiment, when only the triazine-based ultraviolet absorber that is an organic ultraviolet absorber is added, can maintain the transparency of the base resin, but the change with time is unavoidable. There was a possibility that the sustainability of the ultraviolet absorption performance in the period was not sufficient.
Moreover, when only zinc oxide, which is an inorganic ultraviolet absorber, is added, the ultraviolet absorption performance over a long period is good with little change over time, but if added in a large amount, the transparency is lowered and the design of the decorative sheet itself is impaired. There was a possibility.

Furthermore, in both organic and inorganic UV absorbers, if the amount added is increased in order to improve the weather resistance, the aggregated UV absorber increases and UV absorption due to aggregation of the UV absorber is increased. Bleed-out, in which agent bloom (powder spray) or bleed (liquid spray) occurs, is likely to occur, which may cause deterioration in design due to whitening of the sheet surface and adhesion due to stickiness.
As a result of intensive studies, the inventors of the present invention added an organic ultraviolet absorber and an inorganic ultraviolet absorber, and by adding either of them in a vesicle, The present inventors have succeeded in dramatically improving the dispersibility of a UV absorber and an inorganic UV absorber, and found that this can suppress the occurrence of bleed out.

(Fourth embodiment)
The decorative sheet of the present embodiment is a decorative sheet having a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer, and the top coat layer and the transparent resin layer are made of an organic ultraviolet absorber. In particular, it is important that the organic ultraviolet absorber is an organic ultraviolet absorber vesicle included in the outer membrane.

Such an organic ultraviolet absorbent vesicle has a structure in which an organic ultraviolet absorbent is encapsulated in a vesicle-like capsule having a membrane structure closed in a spherical shell shape. This organic ultraviolet absorber vesicle has extremely high dispersibility without particles being aggregated by the action of repelling each other's outer membranes. This action makes it possible to uniformly disperse the organic ultraviolet absorber in the resin composition constituting the top coat layer and the transparent resin layer.

In the decorative sheet of the present embodiment, the organic ultraviolet absorbent vesicle is preferably an organic ultraviolet absorbent liposome having an outer membrane made of phospholipid, and the outer membrane is made of phospholipid. Further, the compatibility between the resin material, which is the main component of the top coat layer and the transparent resin layer, and the vesicle can be improved. In addition, you may make it form the outer membrane of a liposome from the mixture of a phospholipid and a dispersing agent.

In this embodiment, when the organic ultraviolet absorbent vesicle is added to the topcoat layer, it is preferably added in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the topcoat layer forming resin. More preferably, it is 0.5 to 10 parts by weight. When the addition amount of the organic ultraviolet absorbent vesicle is less than 0.1 parts by weight, the effect of ultraviolet absorbing ability is low, and when it is more than 20 parts by weight, the possibility of bleeding out increases. In addition, when such an organic ultraviolet absorber vesicle is added to the transparent resin layer, 0.1 to 10 parts by weight is added to 100 parts by weight of the olefin resin that is the main component of the transparent resin layer. Is preferred. More preferably, it is 0.2 to 5 parts by weight. When the addition amount of the organic ultraviolet absorbent vesicle is less than 0.1 parts by weight, the effect of ultraviolet absorbing ability is low, and when it is more than 10 parts by weight, the possibility of bleeding out increases.

Further, in the decorative sheet of the present embodiment, it is important that the embossed pattern is formed in the transparent resin layer, and at least the top coat layer is embedded in the recess of the embossed pattern. Is preferably provided on the surface of the transparent resin layer so that the top coat layer is embedded in the recess by wiping.
Further, it is important that an ink layer containing at least a light stabilizer is provided in the lower layer of the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, the binder resin itself that forms the ink layer and radicals generated by resin degradation of the other layer reduce the chemical component of the pigment in the ink, thereby fading the pigment. It can suppress and can hold a colorful picture over a long period of time.

In addition, about the organic type ultraviolet absorber used in this embodiment, since the same thing as 1st Embodiment can be used, description is abbreviate | omitted here.
Further, the method for obtaining the organic ultraviolet absorbent vesicle of the present embodiment (the vesicle forming method) is the same as that of the third embodiment, and the description thereof is omitted here. The method for obtaining an organic ultraviolet absorbent vesicle having an outer film made of a single layer film is also the same as that in the third embodiment, and thus the description thereof is omitted here.
In addition, the phospholipid forming the outer membrane of the vesicle and the other substances forming the outer membrane of the vesicle used in the present embodiment can be the same as those in the first embodiment, and thus the description thereof is omitted here. .

Hereinafter, a specific configuration of the decorative sheet of the present embodiment will be described with reference to FIG.
(overall structure)
FIG. 2 shows a specific configuration of the decorative sheet 1 of the present embodiment. The decorative sheet 1 has an adhesive layer 7 on an original resin sheet as an original fabric layer 2 on which an ink layer 3 is applied. It can be obtained by bonding the formed product and the transparent resin layer 4 to which the organic ultraviolet absorber vesicle is added together with the adhesive resin layer 4b by dry lamination or extrusion lamination. As shown in FIG. 2, the decorative sheet 1 of the present embodiment has a resin composition in which the top coat layer 5 contains an organic ultraviolet absorbent vesicle with respect to the recesses of the embossed pattern 4 a formed in the transparent resin layer 4. An object is applied, and the coating liquid is scraped off with a squeegee or the like to be embedded by wiping in which the resin composition is embedded only in the recess. In other words, the decorative sheet 1 of the present embodiment has a top coat layer 5, a transparent resin layer 4 (adhesive resin layer 4b), an adhesive layer 7, an ink layer 3 and an original fabric layer 2 laminated from the surface layer side. Yes. Moreover, in order to improve designability, the embossed pattern 4a is formed in the surface at the side of the topcoat layer 5 of the transparent resin layer 4, and the topcoat layer 5 is formed in the recessed part of the embossed pattern 4a by wiping. It is formed so that a part of the resin composition is embedded. The ink layer 3 includes a pattern layer 3a provided on the adhesive layer 7 side and a solid ink layer 3b.

Further, the configuration of the decorative sheet 1 of the present embodiment may be the same as the configuration of the decorative sheet of the first embodiment.
In addition, about the resin composition etc. which comprise each said layer, the resin composition etc. substantially the same as each layer demonstrated in 1st Embodiment can be used. Therefore, description of the same resin composition and the like as in the first embodiment is omitted here.

In the top coat layer 5 provided on the outermost surface of the decorative sheet 1 of the present embodiment, the organic ultraviolet absorbent vesicle is 0.1 weight with respect to 100 parts by weight of the resin material which is the main component of the top coat layer 5. Parts to 20 parts by weight. In particular, in the present embodiment, it is preferable to use an organic ultraviolet absorbent liposome having an outer membrane made of a phospholipid obtained by a supercritical reverse phase evaporation method as the organic ultraviolet absorbent vesicle.

In the present embodiment, the top coat layer 5 is provided only in the concave portion of the embossed pattern 4a of the transparent resin layer 4. However, the embossed pattern only needs to be embedded in at least the concave portion of the embossed pattern 4a. By forming 4a, high weather resistance can be maintained even in a recess having a thin layer thickness. The topcoat layer 5 may be provided so as to cover the entire surface of the transparent resin layer 4, and providing the topcoat layer 5 so as to cover the entire surface provides the decorative sheet 1 having better weather resistance. be able to.

Further, an embossed pattern 4a is formed on the surface of the transparent resin layer 4 in order to improve the design. The embossed pattern 4a is formed by a method of forming the embossed pattern 4a by applying heat and pressure using an embossed plate having a concavo-convex pattern before forming the top coat layer 5, or when forming a film using an extruder. The embossed pattern 4a can be formed simultaneously with the cooling of the sheet using a cooling roll having an uneven pattern. In addition, the design can be further improved by embedding ink or the like in the recesses of the embossed pattern 4a.

When non-polar polypropylene is used for the transparent resin layer 4, it is preferable to provide an adhesive resin layer 4b when the adhesion between the transparent resin layer 4 and the resin layer disposed on the lower surface is low. As the adhesive resin layer 4b, those obtained by subjecting a resin such as polypropylene, polyethylene, and acrylic to acid modification are preferable, and the layer thickness is desirably 2 μm or more and 20 μm or less from the viewpoint of adhesiveness and heat resistance. The adhesive resin layer 4b is preferably formed by coextrusion laminating with the transparent resin layer 4 from the viewpoint of improving the adhesive strength.

On the lower surface side of the transparent resin layer 4, as shown in FIG. 2, an adhesive layer 7 for further improving the adhesion between the ink layer 3 on the lower surface side and the transparent resin layer 4 is provided. The method of applying the adhesive layer 7 can be selected as appropriate according to the viscosity of the adhesive, etc., but in general, a gravure coat is used, and a gravure is formed on the raw fabric layer 2 side on which the ink layer 3 is applied. After being applied by coating, it is laminated with the transparent resin layer 4 or the adhesive resin layer 4b. The adhesive layer 7 can be omitted when the adhesive strength between the transparent resin layer 4 and the ink layer 3 is sufficiently obtained.
The ink layer 3 includes a pattern layer 3a made of ink to which at least a light stabilizer is added. Further, by providing the solid ink layer 3b on the lower surface side of the design pattern layer 3a, it is possible to provide concealment.

In the solid ink layer 3b, basically, the same material as the ink used for the pattern layer 3a can be used. However, when the ink is a transparent material, an opaque pigment, titanium oxide, iron oxide, or the like is used. be able to. In addition to this, it is possible to provide concealment properties by adding metals such as gold, silver, copper, and aluminum. Generally, flaky aluminum is used.
These ink layers 3 can be directly formed on the original fabric layer 2 by gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, and the like. Moreover, when concealing property is imparted by a metal, it is preferable to use a comma coater, knife coater, lip coater, metal vapor deposition or sputtering method.

For the interface where the resin material or ink is laminated, the surface to be laminated is subjected to corona treatment, ozone treatment, plasma treatment, electron beam in consideration of its adhesiveness before applying the resin material or ink. Adhesion between layers can be improved by performing a lamination process after activating the surface by performing surface treatment such as treatment, ultraviolet treatment, or dichromic acid treatment.

In the decorative sheet 1 of this embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability and cost, the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the topcoat layer. 5 is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 400 μm.

<Effect of this embodiment>
As described above, in the decorative sheet 1 of this embodiment including the top coat layer 5 and the transparent resin layer 4 to which the organic ultraviolet absorbent vesicle is added, the organic ultraviolet absorbent is dispersed extremely uniformly in the resin composition. A top coat layer 5 and a transparent resin layer 4 are provided. For this reason, the decorative sheet has excellent design characteristics without impairing transparency, and achieves high ultraviolet absorption performance even with a small addition amount, and can obtain excellent weather resistance over a long period of time. 1 can be provided.
In addition to this, by realizing high dispersibility of the organic ultraviolet absorber in the resin composition, there is no bleed out caused by the aggregated additive, and there is little stickiness on the surface The decorative sheet 1 can be provided.

Further, as in this embodiment, by using an organic ultraviolet absorber as an organic ultraviolet absorber vesicle, it is possible to meet the demand for adding a large amount of organic ultraviolet absorber, so that the weather resistance is further improved. It is possible to provide a decorative sheet 1 having excellent performance. In addition, by using an organic ultraviolet absorber vesicle, it is possible to maintain the flexibility, impact strength, and planar smoothness required for the decorative sheet, and organic resin is used as the raw material resin for the top coat layer 5. It is possible to obtain an effect that the decorative sheet 1 having excellent design properties can be obtained by suppressing the thickening by adding a UV absorber and embedding the coating liquid in every corner of the concave portion of the embossed pattern 4a. .
Furthermore, in this embodiment, the resin composition which comprises the topcoat layer 5 and the transparent resin layer 4 by using the organic type ultraviolet absorber liposome obtained by the supercritical reverse phase evaporation method as an organic type ultraviolet absorber vesicle. It is possible to disperse the organic ultraviolet absorber very uniformly in the product, and to realize more excellent transparency and ultraviolet absorption performance.

Hereinafter, the effect of this embodiment will be described in more detail.
(1) The decorative sheet 1 of the present embodiment is a decorative sheet including the top coat layer 5 on the outermost layer and the transparent resin layer 4 on the lower surface of the top coat layer 5, and the top coat layer 5 and the transparent resin layer 4. Contains an organic ultraviolet absorber, and the organic ultraviolet absorber is an organic ultraviolet absorber vesicle contained in an outer film.
With such a configuration, the top coat layer 5 containing the organic ultraviolet absorber vesicle and the transparent resin layer 4 provide excellent design and realize long-term weather resistance. It is possible to provide a decorative sheet.

(2) In the decorative sheet 1 of the present embodiment, the outer film of the organic ultraviolet absorbent vesicle may be a single layer film.
With such a configuration, the organic ultraviolet absorber can be uniformly dispersed in the top coat layer 5 and the transparent resin layer 4, so that high transparency is achieved and the design is excellent, and the weather resistance is excellent. A decorative sheet having the properties can be provided.

(3) The decorative sheet 1 of the present embodiment may be an organic ultraviolet absorbent liposome in which the organic ultraviolet absorbent vesicle has an outer membrane made of phospholipid.
With such a configuration, the compatibility with the resin composition that is the main component of the topcoat layer 5 and the transparent resin layer 4 can be improved, and thus high dispersibility of vesicles in the resin composition It is possible to suppress the occurrence of secondary aggregation.

(4) In the decorative sheet 1 of this embodiment, the organic ultraviolet absorber may be composed of at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate.
Such a configuration makes it possible to provide a decorative sheet that maintains high transparency and is excellent in design.

(5) The decorative sheet 1 of the present embodiment may be provided with the embossed pattern 4a formed on the transparent resin layer 4 and the topcoat layer 5 embedded in at least the recess of the embossed pattern 4a.
With such a configuration, the top coat layer 5 to which the organic ultraviolet absorbent vesicle is added also in the concave portion of the embossed pattern 4a in which the film thickness of the transparent resin layer 4 is reduced by forming the embossed pattern 4a. Is embedded, it is possible to provide a decorative sheet that provides weather resistance comparable to other parts.

(6) In the decorative sheet 1 of the present embodiment, an ink layer 3 containing a light stabilizer may be provided in the lower layer of the transparent resin layer 4.
With such a configuration, the radicals generated by the deterioration of the binder resin itself of the ink layer 3 and the other layers reduce the chemical component of the pigment in the ink, thereby suppressing the fading of the pigment over a long period of time. It is possible to provide a decorative sheet capable of realizing excellent design properties.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.
<Preparation of organic UV absorber vesicle>
First, a method for preparing an organic ultraviolet absorbent vesicle used in Examples 4-1 and 4-2 will be described. The supercritical reverse phase evaporation method was used for the preparation of the organic ultraviolet absorber vesicle.
Specifically, in a high-pressure stainless steel container kept at 60 ° C., 100 parts by weight of hexane and 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5 as an organic ultraviolet absorber. -Triazin-2-yl) -5-hydroxyphenyl as a main component Hydroxyphenyltriazine (TINUVIN400; manufactured by BASF) 70 parts by weight and phosphatidylcholine 5 parts by weight as phospholipid were sealed and sealed. Carbon dioxide is injected so that the pressure becomes 20 MPa to be in a supercritical state, 100 parts by weight of ethyl acetate is injected while stirring vigorously, and after stirring and mixing for 15 minutes while maintaining the temperature and pressure, carbon dioxide is discharged. Was returned to atmospheric pressure. Thus, a hydroxyphenyltriazine liposome having a monolayer outer membrane made of phospholipid was obtained.

<Method for producing decorative sheet 1>
First, with respect to 100 parts by weight of a highly crystalline homopolypropylene resin, 0.5 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF), and a hindered amine light stabilizer (Kimasorb 944; BASF) The resin added with 0.2 part by weight was melt-extruded using an extruder to form a sheet-like transparent resin layer 4 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. Corona treatment was applied to both surfaces of the transparent resin layer 4 thus obtained, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, a pattern is printed on one side of a concealing 70 μm polyethylene sheet (raw fabric layer 2) using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) by gravure printing. The layer 3a was provided, and a primer coat was applied to the other surface of the original fabric layer 2. Thereafter, on the surface of the pattern layer 3a of the original fabric layer 2, an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals; application amount 2 g / m ² ) using the transparent resin layer 4 as an adhesive layer 7 is applied. And bonded together by a dry laminating method. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the bonded sheet, and then a two-component urethane top coat (W184; manufactured by DIC Graphics) is applied at a coating thickness of 3 g / m ² to form a top coat. Layer 5 was formed. Thus, the decorative sheet 1 of the present embodiment having a total thickness of 157 μm was obtained.

<Example 4-1>
In Example 4-1, the 100 parts by weight of the two-component urethane topcoat that is the main component of the topcoat layer 5 and 100 parts by weight of the highly crystalline polypropylene resin that is the main component of the transparent resin layer 4 are used. The decorative sheet 1 was provided with a top coat layer 5 and a transparent resin layer 4 to which hydroxyphenyltriazine liposomes were added at a ratio of 0.2, 1.0, 2.5, or 10.0, respectively.

<Example 4-2>
In Example 4-2, 100 parts by weight of the two-component urethane topcoat that is the main component of the topcoat layer 5 and 100 parts by weight of the highly crystalline polypropylene resin that is the main component of the transparent resin layer 4 are used. A hindered amine light stabilizer (Kimasorb 944; BASF) is added to 100 parts by weight of the topcoat layer 5 and the transparent resin layer 4 and the two-component urethane ink to which the hydroxyphenyltriazine liposome is added at a ratio of 0.2 or 10.0, respectively. The decorative sheet 1 was provided with a pattern layer 3a to which 0.2% by weight was added. Other configurations are the same as those in the embodiment 4-1.

<Comparative Example 4-1>
In Comparative Example 4-1, 100 parts by weight of the two-component urethane topcoat that is the main component of the topcoat layer 5 and 100 parts by weight of the highly crystalline polypropylene resin that is the main component of the transparent resin layer 4 are vesicled. A decorative sheet 1 having a topcoat layer 5 and a transparent resin layer 4 to which hydroxyphenyltriazine not added was added at a ratio of 0.2, 1.0, or 10.0, respectively. Other configurations are the same as those in the embodiment 4-1.

<Comparative Example 4-2>
In Comparative Example 4-2, the decorative sheet 1 was provided with the top coat layer 5 and the transparent resin layer 4 to which no organic ultraviolet absorber was added. Other configurations are the same as those in the embodiment 4-1.

<Evaluation>
For each decorative sheet 1 of Examples 4-1 and 4-2 and Comparative Examples 4-1 and 4-2 obtained by the above method, the ultraviolet absorbing ability and the haze value were the same as in the first embodiment. The color change (ΔE) and the appearance change after the weather resistance test were evaluated. The obtained evaluation results are shown in Table 11. Note that the meaning of the sign of appearance change is the same as in the first embodiment.

In the decorative sheet 1 of Example 4-1, as shown in Table 11, as the added amount of the hydroxyphenyltriazine liposome increases, the value of the color difference (ΔE) before and after the ultraviolet absorption ability and the weather resistance test becomes smaller. The haze value showed a large value. This is presumably because the weather resistance was improved when the amount of the hydroxyphenyltriazine liposome added was increased, while the haze value was increased due to white turbidity caused by the additive.

In the decorative sheet 1 of Example 4-2, as shown in Table 11, the value of the color difference (ΔE) before and after the ultraviolet absorption ability and the weather resistance test decreases as the addition amount of the hydroxyphenyltriazine liposome increases. The haze value was a large value, which was similar to that of the decorative sheet 1 of Example 4-1. In particular, in the decorative sheet 1 of Example 4-2, the value of the color difference (ΔE) before and after the weather resistance test is very small, and the amount of the hydroxyphenyl triazine liposome added in Example 4-1 is the same amount. Compared to the value of the color difference (ΔE) of the decorative sheet 1, which is a small value, this is an ink that forms a picture pattern by adding a light stabilizer to the picture pattern layer 3 a. This is thought to be due to the suppression of decolorization.

In the decorative sheet 1 of Comparative Example 4-1, as shown in Table 11, when compared with the decorative sheet 1 of Examples 4-1 and 4-2, the UV difference, haze value, and color difference before and after the weather resistance test ( The value of ΔE) shows a large value, and it can be seen that the weather resistance and design properties are poor. In particular, for the decorative sheet 1 in which the amount of hydroxyphenyltriazine added was 0.2 parts by weight, sufficient ultraviolet absorption performance was not obtained, and thus whitening and cracking were observed after the weather resistance test. This is because the hydroxyphenyltriazine is not vesicled, and the hydroxyphenyltriazine aggregates in the resin composition to cause white turbidity, and the surface area of the UV absorber is reduced by the aggregation and sufficient UV absorption is achieved. This is probably because the performance was not demonstrated. In addition, the decorative sheet 1 in which the amount of hydroxyphenyltriazine added is 10.0 parts by weight, although the amount of hydroxyphenyltriazine added is large, the change in appearance after the weather resistance test was slight. The white turbidity resulting from the aggregation of the additive was remarkable, resulting in poor design. In the decorative sheet 1 of Comparative Example 4-2, as shown in Table 11, compared with the decorative sheets 1 of Examples 4-1 and 4-2 and Comparative Example 4-1, the ultraviolet absorbing ability and the weather resistance It can be seen that the color difference (ΔE) before and after the test is extremely large and has almost no weather resistance.

From the above results, it was revealed that the decorative sheets 1 of Examples 4-1 and 4-2 were excellent in weather resistance and design properties. Furthermore, it became clear that a colorful pattern can be maintained over a long period of time by providing the pattern layer 3a to which a light stabilizer is added.

[Reference example]
Hereinafter, a decorative sheet other than the decorative sheet described in the present embodiment will be briefly described as a reference example of the present invention.
When the decorative sheet other than the decorative sheet described in the present embodiment contains an organic ultraviolet absorber in an amount sufficient to provide sufficient weather resistance, the organic sheet is included in the resin composition constituting the resin layer such as the top coat layer. Aggregation of the UV absorber occurs, but the design of the decorative sheet may be impaired if the aggregation occurs particularly in a resin layer that requires transparency, such as a transparent layer composed of a topcoat layer and a transparent resin layer. There was sex.

In addition, when the aggregation of the organic ultraviolet absorber occurs in the resin composition, a bleed out that the organic ultraviolet absorber aggregated from the surface of the resin layer is likely to occur, and with the occurrence of the bleed out, In the topcoat layer, the sheet surface may become sticky, and in the transparent resin layer, the adhesion with other resin layers may be lowered.
In addition to this, when an embossed pattern is formed in order to improve the design of the decorative sheet, the concave portion of the embossed pattern becomes thinner than the other parts, so the weather resistance is particularly low, There was a possibility that the deterioration started from the recess and whitening or breakage occurred.
As a result of intensive studies, the present inventors have succeeded in dramatically improving the dispersibility of the organic ultraviolet absorber in the resin material by including the organic ultraviolet absorber in a state of being included in the vesicle. It has been found that the transparency required for the decorative sheet can be achieved.

(Fifth embodiment)
The decorative sheet of the present embodiment is a decorative sheet including a transparent resin layer made of a transparent olefin resin, and the transparent resin layer contains an organic ultraviolet absorber, and the organic ultraviolet absorber is a simple substance. It is important that the organic ultraviolet absorber vesicle has an outer film composed of a layer film.
Such an organic ultraviolet absorber vesicle has a structure in which an organic ultraviolet absorber is encapsulated in a vesicular capsule having a membrane structure closed in a spherical shell shape. This organic ultraviolet absorber vesicle has extremely high dispersibility without particles being aggregated by the action of repelling each other's outer membranes. This action enables the organic ultraviolet absorber to be uniformly dispersed in the resin composition constituting the transparent resin layer.

In the decorative sheet of the present embodiment, the organic ultraviolet absorbent vesicle is preferably an organic ultraviolet absorbent liposome having an outer membrane made of phospholipid, and the outer membrane is made of phospholipid. The compatibility between the resin material, which is the main component of the transparent resin layer, and the vesicle can be improved. In addition, you may make it form the outer membrane of a liposome from the mixture of a phospholipid and a dispersing agent.

Further, in this embodiment, when the organic ultraviolet absorber vesicle is added to the transparent resin layer, the proportion is 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin material as the main component of the transparent resin layer. It is preferable to add, and more preferably 0.2 to 5 parts by weight. If the addition amount of the organic UV absorber is less than 0.1 parts by weight, sufficient UV absorption performance cannot be obtained. If the addition amount is more than 10 parts by weight, the possibility of bleeding out increases. .

Further, it is important that an ink layer to which at least a light stabilizer is added is provided under the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, the binder resin itself that forms the ink layer and radicals generated by resin degradation of the other layer reduce the chemical component of the pigment in the ink, thereby fading the pigment. It can suppress and can hold a colorful picture over a long period of time.
Further, a top coat layer may be provided on the upper surface of the transparent resin layer according to the application and required characteristics. In particular, in applications that require mechanical strength, it is important that a topcoat layer is provided.

In addition, about the organic type ultraviolet absorber used in this embodiment, since the same thing as 1st Embodiment can be used, description is abbreviate | omitted here.
Further, the method for obtaining the organic ultraviolet absorbent vesicle of the present embodiment (the vesicle forming method) is the same as that of the third embodiment, and the description thereof is omitted here. The method for obtaining an organic ultraviolet absorbent vesicle having an outer film made of a single layer film is also the same as that in the third embodiment, and thus the description thereof is omitted here.
In addition, the phospholipid forming the outer membrane of the vesicle and the other substances forming the outer membrane of the vesicle used in the present embodiment can be the same as those in the first embodiment, and thus the description thereof is omitted here. .

Hereinafter, a specific configuration of the decorative sheet of the present embodiment will be described with reference to FIG.
(overall structure)
FIG. 1 shows a specific configuration of the decorative sheet 1 of the present embodiment, and the decorative sheet 1 is composed of a plurality of resin layers. In the decorative sheet 1 of the present embodiment, a top coat layer 5, a transparent resin layer 4, an adhesive layer 7, an ink layer 3 and an original fabric layer 2 are laminated from the surface layer side. Moreover, in order to improve the designability, the embossed pattern 4a is formed on the surface of the transparent resin layer 4 on the topcoat layer 5 side, and the topcoat layer 5 is formed by wiping in the concave portion of the embossed pattern 4a. A resin composition is embedded and provided. The adhesive layer 7 is made of, for example, a heat sensitive adhesive, an anchor coat, a dry lamination adhesive, or the like. Moreover, the decorative sheet is formed by adhering the decorative sheet 1 to the base material B. The base material B is a wood board, an inorganic board, a metal plate, or the like.
In addition, about the resin composition etc. which comprise each said layer, the resin composition etc. substantially the same as each layer demonstrated in 1st Embodiment can be used. Therefore, description of the same resin composition and the like as in the first embodiment is omitted here.

In the present embodiment, as the transparent resin layer 4, a resin composition containing an olefin resin as a main component and an organic ultraviolet absorber vesicle can be used.
In the decorative sheet 1 of the present embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability and cost, the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the top. The coat layer 5 is desirably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 400 μm.

<Effect of this embodiment>
Thus, in the decorative sheet 1 of this embodiment, the organic ultraviolet absorber is included in the resin composition constituting the transparent resin layer 4 by including the transparent resin layer 4 to which the organic ultraviolet absorber vesicle is added. Realizes a transparent resin layer 4 in which is uniformly dispersed. As a result, it is possible to provide a decorative sheet 1 that has excellent weather resistance without unnecessarily increasing the addition amount, and that realizes high transparency and excellent design.

In addition to this, as in this embodiment, by using an organic ultraviolet absorber as an organic ultraviolet absorber vesicle, the demand for adding a large amount of organic ultraviolet absorber without causing bleed-out is also met. Therefore, it is possible to provide the decorative sheet 1 having further excellent weather resistance.
Furthermore, by making the ink layer 3 to which a light stabilizer is added, it is possible to suppress fading of the ink layer 3 by ultraviolet rays, and make-up with excellent design properties that retains beautiful color prints over a long period of time. Sheet 1 can be provided.

Hereinafter, the effect of this embodiment will be described in more detail.
(1) The decorative sheet 1 of the present embodiment is a decorative sheet including a transparent resin layer 4 made of a transparent olefin resin, and the transparent resin layer 4 contains an organic ultraviolet absorber. The organic ultraviolet absorber is an organic ultraviolet absorber vesicle having an outer film made of a single layer film.
With such a configuration, the organic ultraviolet absorber can be uniformly dispersed in the transparent resin layer 4, so that high transparency is achieved, the design is excellent, and the makeup has excellent weather resistance. Sheets can be provided.

(2) In the decorative sheet 1 of this embodiment, the organic ultraviolet absorber may be composed of at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate.
With such a configuration, it is possible to provide a decorative sheet with more excellent design without impairing the transparency of the topcoat layer 5 as compared with the case where an inorganic ultraviolet absorber is used.

(3) The decorative sheet 1 of the present embodiment may be a liposome having an outer membrane whose vesicle is made of phospholipid.
If it is such a structure, compatibility with the resin composition of the main component of the topcoat layer 5 can be made favorable.

(4) In the decorative sheet 1 of this embodiment, an ink layer containing a light stabilizer may be provided in the lower layer of the transparent resin layer 4.
With such a configuration, the radicals generated by the deterioration of the binder resin itself of the ink layer 3 and the other layers reduce the chemical component of the pigment in the ink, thereby suppressing the fading of the pigment over a long period of time. It is possible to provide a decorative sheet capable of realizing excellent design properties.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.

<Preparation of organic UV absorber vesicle>
Hereinafter, a method for preparing an organic ultraviolet absorbent vesicle will be described. The supercritical reverse phase evaporation method was used for the preparation of the organic ultraviolet absorber vesicle.
The organic ultraviolet absorber vesicle was prepared by adding 100 parts by weight of 2-propanol and triazine ultraviolet absorber 2- (4,6-- as an organic ultraviolet absorber) to a high-pressure stainless steel container kept at 60 ° C. As a phospholipid and 70 parts by weight of hydroxyphenyltriazine (TINUVIN 400; manufactured by BASF) mainly composed of bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl 5 parts by weight of phosphatidylcholine was sealed, carbon dioxide was injected so that the pressure in the container was 20 MPa, and the mixture was brought into a supercritical state, and 100 parts by weight of ion-exchanged water was injected with vigorous stirring and mixing. The mixture was stirred and mixed for 15 minutes while maintaining the pressure, and then carbon dioxide was discharged to return to atmospheric pressure. Thus, triazine-based ultraviolet absorbent liposomes having a monolayer outer membrane made of phospholipid were obtained.

<Method for producing decorative sheet 1>
0.05 parts by weight of hindered phenolic antioxidant (Irganox 1010; manufactured by BASF), 0.2 parts by weight of hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) in homopolypropylene resin, Transparent high-crystalline polypropylene having a thickness of 80 μm is obtained by melt-extruding a resin added with triazine-based UV absorber liposome or organic UV absorber in the addition amount shown in Examples or Comparative Examples using an extruder. A sheet-like transparent resin layer 4 as a sheet was formed. Corona treatment was applied to both surfaces of the transparent resin layer 4 thus obtained, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, an ink layer is printed on one surface of a concealing 70 μm polyethylene sheet (raw fabric layer 2) by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.). 3 and a primer coat was applied to the other side of the original fabric layer 2. Thereafter, on the surface of the ink layer 3 formed on the original fabric layer 2, an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc.) using the transparent resin layer 4 as an adhesive layer 7; coating amount 2 g / m ² ) Through a dry lamination method. Thus, a laminated resin sheet composed of the raw fabric layer 2, the ink layer 3, the adhesive layer 7, and the transparent resin layer 4 was obtained. Then, the embossed pattern 4a was given to the surface of the transparent resin layer 4 of this laminated resin sheet, and the decorative sheet 1 with a total thickness of 157 μm was obtained.

<Example 5-1>
In Example 5-1, with respect to 100 parts by weight of the highly crystalline homopolypropylene resin that is the main component of the transparent resin layer 4, the triazine-based ultraviolet absorbent liposome prepared by the above-described method was added in an amount of 0.2, 1.0. , 5.0 or 10.0 parts by weight of the decorative sheet 1 provided with the transparent resin layer 4 added.

<Example 5-2>
In Example 5-2, 0.2 or 10.0 of the triazine-based ultraviolet absorbent liposome prepared by the above-described method was added to 100 parts by weight of the highly crystalline homopolypropylene resin which is the main component of the transparent resin layer 4. The transparent resin layer 4 added at a ratio of parts by weight, and the ink layer 3 added with a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) at a ratio of 0.2 parts by weight with respect to 100 parts by weight of the ink. The decorative sheet 1 was provided.

<Comparative Example 5-1>
In Comparative Example 5-1, the triazine-based ultraviolet absorber that was not vesicled was added to 0.2, 1.0, or 10 with respect to 100 parts by weight of the highly crystalline homopolypropylene resin that is the main component of the transparent resin layer 4. It was set as the decorative sheet 1 which comprises the transparent resin layer 4 added in the ratio of 0 weight part.

<Comparative Example 5-2>
In Comparative Example 5-2, the decorative sheet 1 was provided with the transparent resin layer 4 to which no organic ultraviolet absorber was added.

<Evaluation>
For each decorative sheet 1 of Examples 5-1 and 5-2 and Comparative Examples 5-1 and 5-2 obtained by the above method, the ultraviolet absorptivity and haze value were obtained in the same manner as in the first embodiment. The color change (ΔE) and the appearance change after the weather resistance test were evaluated. Table 12 shows the obtained evaluation results. Note that the meaning of the sign of appearance change is the same as in the first embodiment.

In the decorative sheet 1 of Example 5-1, as shown in Table 12, the UV absorption ability value and the color difference (ΔE) values before and after the weather resistance test are small for any sample added. Thus, it can be seen that the film has excellent ultraviolet absorption performance and hardly undergoes color change due to deterioration. Moreover, it became clear from the haze value after a weather resistance test that the transparent resin layer 4 maintains transparency required for the decorative sheet even after the test.

In addition, as shown in Table 12, the decorative sheet 1 of Example 5-2 has a UV absorption capability that is small before and after the weather resistance test with a small value of UV absorption capability. From the haze value after the weather resistance test, it became clear that the transparent resin layer 4 maintained the transparency required for the decorative sheet even after the test. In the decorative sheet 1 of Example 5-2, it can be seen that the color difference (ΔE) before and after the weather resistance test is particularly small and the color change due to deterioration is extremely small. This is considered to be because the decolorization of the ink layer during the weather resistance test was suppressed because the ink layer 3 to which the light stabilizer was added was provided.

In the decorative sheet 1 of Comparative Example 5-1, as shown in Table 12, Example 5 shows all of the values of the ultraviolet absorbing ability, the haze value after the weather resistance test, and the color difference (ΔE) before and after the weather resistance test. The values are larger than the respective values of -1, 5-2, and it is understood that sufficient ultraviolet absorption performance is not obtained. From the result of the appearance change, whitening and cracks occurred after the weather resistance test. This is because an organic ultraviolet absorber that has not been vesicled is used, and the organic ultraviolet absorber aggregates in the resin composition constituting the transparent resin layer 4 and sufficient ultraviolet absorption performance cannot be obtained. It is considered that the resin composition is greatly deteriorated and transparency is lowered due to the aggregated ultraviolet absorber. In the decorative sheet 1 of Comparative Example 5-2, as shown in Table 12, it can be seen that the value of the color difference (ΔE) before and after the ultraviolet absorption ability and the weather resistance test is extremely large, and it has no ultraviolet absorption performance at all. . From the result of the appearance change, it can be seen that severe whitening and breakage occur after the weather resistance test. Although the haze value after the weather resistance test shows a small value, this is because the organic ultraviolet absorber is not added to the transparent resin layer 4 and the white turbidity caused by the additive does not occur. It is.

From this evaluation result, the decorative sheet 1 in Examples 5-1 and 5-2 includes the transparent resin layer 4 to which the organic ultraviolet absorbent liposome is added, and thus has excellent ultraviolet absorption performance over a long period of time. It was revealed that this resin can continue to be expressed, and this excellent ultraviolet light absorption performance can prevent whitening of the resin and maintain excellent transparency over a long period of time. Moreover, it becomes clear that by using the ink layer 3 to which a light stabilizer is added, it is possible to prevent the fading of the ink that cannot be prevented by the ultraviolet absorber, and to maintain the decorative sheet 1 having excellent design properties over a long period of time. It was.

[Reference example]
Hereinafter, a decorative sheet other than the decorative sheet described in the present embodiment will be briefly described as a reference example of the present invention.
In a decorative sheet other than the decorative sheet described in the present embodiment, when the method described in Patent Document 1 is applied to a transparent resin layer, the olefin resin forming the transparent resin layer is nonpolar, typified by polyethylene or polypropylene. In order to obtain sufficient weather resistance, it is necessary to add a large amount of the organic ultraviolet absorber, but the compatibility with the organic ultraviolet absorber having polarity is poor. When added, aggregation may occur and the transparency of the transparent resin layer may be impaired.

In particular, in the case of organic UV absorbers, the agglomerated UV absorber may bleed out, resulting in stickiness on the surface of the decorative sheet and the possibility of lowering the adhesion with the top coat layer formed on the transparent resin layer. there were.
As a result of intensive studies, the present inventors have found that by using a vesicle-shaped organic ultraviolet absorber, exceptional weather resistance can be obtained even with an addition amount that is not different from the conventional amount.

(Sixth embodiment)
The decorative sheet of the present embodiment is a decorative sheet having a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer, and at least one of the top coat layer and the transparent resin layer is an inorganic ultraviolet ray In particular, it is important that the inorganic ultraviolet absorbent vesicle contains an absorbent, and the inorganic ultraviolet absorbent is included in the outer membrane.

Such an inorganic ultraviolet absorber vesicle has a structure in which an inorganic ultraviolet absorber is encapsulated in a vesicular capsule having a membrane structure closed in a spherical shell shape. This inorganic ultraviolet absorber vesicle has extremely high dispersibility without particles being aggregated by the action of repelling each other's outer membranes. This action makes it possible to uniformly disperse the inorganic ultraviolet absorber in the resin composition constituting the top coat layer and the transparent resin layer.

In the decorative sheet of this embodiment, the inorganic ultraviolet absorbent vesicle is preferably an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid, and the outer membrane is made of phospholipid. The compatibility between the resin material, which is the main component of at least one of the topcoat layer and the transparent resin layer, and the vesicle can be improved. In addition, you may make it form the outer membrane of a liposome from the mixture of a phospholipid and a dispersing agent.

Further, the inorganic ultraviolet absorber is preferably added in the topcoat layer at a ratio of 0.5 to 20 parts by weight with respect to 100 parts by weight of the resin material as the main component of the topcoat layer. Preferably, it is added at a ratio of 1 to 10 parts by weight, and more preferably at a ratio of 3 to 5 parts by weight. Further, in the transparent resin layer, it is preferably added in a proportion of 0.01 to 5.0 parts by weight, more preferably 0.2 parts by weight with respect to the resin material that is the main component of the transparent resin layer. That is, it is added in a ratio of parts by weight to 3.0 parts by weight. By setting the inorganic ultraviolet absorber to the above-described addition amount, it is possible to realize a decorative sheet having both particularly excellent weather resistance and design.

Further, in the decorative sheet of the present embodiment, it is important that the embossed pattern is formed in the transparent resin layer, and at least the top coat layer is embedded in the recess of the embossed pattern. Is preferably provided on the surface of the transparent resin layer so that the top coat layer is embedded in the recess by wiping.
Further, it is important that an ink layer to which at least a light stabilizer is added is provided under the transparent resin layer. As the light stabilizer, it is preferable to use a hindered amine material. By adding a light stabilizer to the ink layer, the binder resin itself that forms the ink layer and radicals generated by resin degradation of the other layer reduce the chemical component of the pigment in the ink, thereby fading the pigment. It can suppress and can hold a colorful picture over a long period of time.

In addition, about the inorganic type ultraviolet absorber used in this embodiment, since the same thing as 1st Embodiment can be used, description is abbreviate | omitted here.
In addition, the method for obtaining the inorganic ultraviolet absorbent vesicle (the vesicle forming method) of the present embodiment is the same as that of the third embodiment, and thus the description thereof is omitted here. The method for obtaining an inorganic ultraviolet absorbent vesicle having an outer film made of a single-layer film is also the same as that in the third embodiment, and a description thereof is omitted here.
In addition, the phospholipid forming the outer membrane of the vesicle and the other substances forming the outer membrane of the vesicle used in the present embodiment can be the same as those in the first embodiment, and thus the description thereof is omitted here. .

Hereinafter, a specific embodiment of the decorative sheet of the present embodiment will be described with reference to FIG.

FIG. 2 shows a specific configuration of the decorative sheet 1 of the present embodiment. The decorative sheet 1 has an adhesive layer 7 on an original resin sheet as an original fabric layer 2 on which an ink layer 3 is applied. It can be obtained by bonding the formed product and the transparent resin layer 4 to which the inorganic ultraviolet absorber vesicle is added together with the adhesive resin layer 4b by dry lamination or extrusion lamination. As shown in FIG. 2, the decorative sheet 1 of the present embodiment has a resin composition in which the top coat layer 5 contains an inorganic ultraviolet absorbent vesicle with respect to the concave portion of the embossed pattern 4 a formed in the transparent resin layer 4. An object is applied, and the coating liquid is scraped off with a squeegee or the like to be embedded by wiping in which the resin composition is embedded only in the recess. In other words, the decorative sheet 1 of the present embodiment has a top coat layer 5, a transparent resin layer 4 (adhesive resin layer 4b), an adhesive layer 7, an ink layer 3 and an original fabric layer 2 laminated from the surface layer side. Yes. Moreover, in order to improve designability, the embossed pattern 4a is formed in the surface at the side of the topcoat layer 5 of the transparent resin layer 4, and the topcoat layer 5 is formed in the recessed part of the embossed pattern 4a by wiping. It is formed so that a part of the resin composition is embedded. The ink layer 3 includes a pattern layer 3a provided on the adhesive layer 7 side and a solid ink layer 3b.

Further, the configuration of the decorative sheet 1 of the present embodiment may be the same as the configuration of the decorative sheet of the first embodiment.
In addition, about the resin composition etc. which comprise each said layer, the resin composition etc. substantially the same as each layer demonstrated in 1st Embodiment can be used. Therefore, description of the same resin composition and the like as in the first embodiment is omitted here.

In the top coat layer 5 provided on the outermost surface of the decorative sheet 1 of the present embodiment, the inorganic ultraviolet absorbent vesicle is 0.5 weight with respect to 100 parts by weight of the resin material which is the main component of the top coat layer 5. Parts to 20 parts by weight. In particular, in the present embodiment, it is preferable to use an inorganic ultraviolet absorbent liposome having an outer membrane made of a phospholipid obtained by a supercritical reverse phase evaporation method as the inorganic ultraviolet absorbent vesicle.

In the present embodiment, the top coat layer 5 is provided only in the concave portion of the embossed pattern 4a of the transparent resin layer 4. However, the embossed pattern only needs to be embedded in at least the concave portion of the embossed pattern 4a. By forming 4a, high weather resistance can be maintained even in a recess having a thin layer thickness. The topcoat layer 5 may be provided so as to cover the entire surface of the transparent resin layer 4, and providing the topcoat layer 5 so as to cover the entire surface provides the decorative sheet 1 having better weather resistance. be able to.

In the present embodiment, the transparent resin layer 4 is composed of a resin composition containing the above-described resin material as a main component and containing an inorganic ultraviolet absorbent vesicle obtained by a supercritical reverse phase evaporation method. The inorganic ultraviolet absorbent vesicle is preferably contained in a proportion of 0.1 to 5.0 parts by weight with respect to the resin material which is the main component of the transparent resin layer 4. In particular, in this embodiment, an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid obtained by a supercritical reverse phase evaporation method is used as the inorganic ultraviolet absorbent vesicle.

Further, an embossed pattern 4a is formed on the surface of the transparent resin layer 4 in order to improve the design. The embossed pattern 4a is formed by a method of forming the embossed pattern 4a by applying heat and pressure using an embossed plate having a concavo-convex pattern before forming the top coat layer 5, or when forming a film using an extruder. The embossed pattern 4a can be formed simultaneously with the cooling of the sheet using a cooling roll having an uneven pattern. In addition, the design can be further improved by embedding ink or the like in the recesses of the embossed pattern 4a.

When non-polar polypropylene is used for the transparent resin layer 4, it is preferable to provide an adhesive resin layer 4b when the adhesion between the transparent resin layer 4 and the resin layer disposed on the lower surface is low. As the adhesive resin layer 4b, those obtained by subjecting a resin such as polypropylene, polyethylene, and acrylic to acid modification are preferable, and the layer thickness is desirably 2 μm or more and 20 μm or less from the viewpoint of adhesiveness and heat resistance. The adhesive resin layer 4b is preferably formed by coextrusion laminating with the transparent resin layer 4 from the viewpoint of improving the adhesive strength.

On the lower surface side of the transparent resin layer 4, as shown in FIG. 2, an adhesive layer 7 for further improving the adhesion between the ink layer 3 on the lower surface side and the transparent resin layer 4 is provided. The method of applying the adhesive layer 7 can be selected as appropriate according to the viscosity of the adhesive, etc., but in general, a gravure coat is used, and the gravure layer 2 side on which the ink layer 3 is applied is gravure. After being applied by coating, it is laminated with the transparent resin layer 4 or the adhesive resin layer 4b. The adhesive layer 7 can be omitted when the adhesive strength between the transparent resin layer 4 and the ink layer 3 is sufficiently obtained.

The ink layer 3 includes a pattern layer 3a made of ink to which at least a light stabilizer is added. Further, by providing the solid ink layer 3b on the lower surface side of the design pattern layer 3a, it is possible to provide concealment.
In the present embodiment, both the top coat layer 5 and the transparent resin layer 4 contain an inorganic ultraviolet absorbent vesicle, but either one contains an inorganic ultraviolet absorbent vesicle. A configuration may be adopted.

In the decorative sheet 1 of the present embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability and cost, the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the top. The coat layer 5 is desirably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 400 μm.
The above-described solid ink layer 3b has been described in the fourth embodiment, and thus the description thereof is omitted here.

<Effect of this embodiment>
As described above, in the decorative sheet 1 of this embodiment including at least one of the topcoat layer 5 and the transparent resin layer 4 containing the inorganic ultraviolet absorbent vesicle, the inorganic ultraviolet absorbent is extremely uniform in the resin composition. As a result, at least one of the top coat layer 5 and the transparent resin layer 4 dispersed in the material is realized, and as a result, the transparency is not impaired and excellent design is provided, and even at a low content, high UV absorption is achieved. It is possible to provide a decorative sheet 1 that achieves performance and can obtain excellent weather resistance over a long period of time.
In addition to this, by realizing high dispersibility of the inorganic ultraviolet absorber in the resin composition, there is no bleed out caused by the aggregated additive, and there is little stickiness on the surface The decorative sheet 1 can be provided.

In addition, as in this embodiment, by using an inorganic ultraviolet absorber as an inorganic ultraviolet absorber vesicle, it is possible to meet the demand for containing a large amount of an inorganic ultraviolet absorber, and even more, It is possible to provide the decorative sheet 1 having excellent weather resistance. In addition, by using an inorganic ultraviolet absorber vesicle, the effect that the flexibility, impact strength, and flatness required for the decorative sheet can be maintained, and the material resin of the topcoat layer 5 is inorganic. It is possible to obtain an effect that the decorative sheet 1 having excellent design properties can be obtained by suppressing the thickening by adding a UV absorber and embedding the coating liquid in every corner of the concave portion of the embossed pattern 4a. .

Furthermore, in this embodiment, at least one of the top coat layer 5 and the transparent resin layer 4 is configured by using an inorganic ultraviolet absorbent liposome obtained by a supercritical reverse phase evaporation method as the inorganic ultraviolet absorbent vesicle. In the resin composition, it is possible to disperse the inorganic ultraviolet absorber very uniformly, and it is possible to realize more excellent transparency and ultraviolet absorption performance.

Hereinafter, the effect of this embodiment will be described in more detail.
(1) The decorative sheet 1 of the present embodiment is a decorative sheet including the top coat layer 5 on the outermost layer and the transparent resin layer 4 on the lower surface of the top coat layer 5, and the top coat layer 5 and the transparent resin layer 4. At least one of these contains an inorganic ultraviolet absorber, and the inorganic ultraviolet absorber contained is an inorganic ultraviolet absorber vesicle included in an outer film.
With such a configuration, by providing at least one of the topcoat layer 5 and the transparent resin layer 4 containing an inorganic ultraviolet absorber vesicle, it has excellent design and weather resistance over a long period of time. It is possible to provide a decorative sheet that realizes the performance.

(2) In the decorative sheet 1 of the present embodiment, the outer film of the inorganic ultraviolet absorbent vesicle may be a single layer film.
With such a configuration, the inorganic ultraviolet absorber can be uniformly dispersed in at least one of the top coat layer 5 and the transparent resin layer 4, so that high transparency is achieved and the design is excellent, and the A decorative sheet having excellent weather resistance can be provided.

(3) The decorative sheet 1 of the present embodiment may be an inorganic ultraviolet absorbent liposome in which the inorganic ultraviolet absorbent vesicle has an outer membrane made of phospholipid.
With such a configuration, the compatibility with the resin composition that is the main component of at least one of the top coat layer 5 and the transparent resin layer 4 can be improved. High dispersibility is realized, and it is possible to suppress the occurrence of secondary aggregation.

(4) In the decorative sheet 1 of the present embodiment, the inorganic ultraviolet absorber may be zinc oxide.
Such a configuration makes it possible to provide a decorative sheet that maintains high transparency and is excellent in design.

(5) The decorative sheet 1 of the present embodiment may be provided with the embossed pattern 4a formed on the transparent resin layer 4 and the topcoat layer 5 embedded in at least the recess of the embossed pattern 4a.
In such a configuration, the top coat layer 5 is embedded in the concave portion of the embossed pattern 4a in which the film thickness of the transparent resin layer 4 is reduced by forming the embossed pattern 4a. It is possible to provide a decorative sheet that provides weather resistance not inferior to the above.

(6) In the decorative sheet 1 of the present embodiment, an ink layer containing a light stabilizer may be provided in the lower layer of the transparent resin layer 4.
With such a configuration, the radicals generated by the deterioration of the binder resin itself of the ink layer 3 and the other layers reduce the chemical component of the pigment in the ink, thereby suppressing the fading of the pigment over a long period of time. It is possible to provide a decorative sheet capable of realizing excellent design properties.

[Example]
Hereinafter, specific examples of the decorative sheet 1 of the present embodiment will be described.

<Preparation 1 of Inorganic UV Absorber Vesicle>
First, a method for preparing an inorganic ultraviolet absorbent vesicle used in Examples 6-1 and 6-2 will be described. The supercritical reverse phase evaporation method was used for the preparation of inorganic UV absorber vesicles.
Specifically, 100 parts by weight of 2-propanol, 70 parts by weight of zinc oxide as an inorganic ultraviolet absorber, and 5 parts by weight of phosphatidylcholine as a phospholipid are sealed in a high-pressure stainless steel container kept at 60 ° C. Then, carbon dioxide is injected so that the pressure in the container becomes 20 MPa to be in a supercritical state, and 100 parts by weight of ion-exchanged water is injected with vigorous stirring and mixing, followed by stirring and mixing for 15 minutes while maintaining the temperature and pressure. The carbon dioxide was discharged and returned to atmospheric pressure. Thus, zinc oxide liposomes having a monolayer outer membrane made of phospholipid were obtained.

<Example 6-1>
In Example 6-1, the decorative sheet 1 was provided with the transparent resin layer 4 containing the zinc oxide liposome prepared in <Preparation 1 of inorganic ultraviolet absorbent vesicle> described above.

Specifically, 0.05 parts by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and 0.05, 0.1, 0.2, 3. 0, 5.0, 15.0 parts by weight, a resin added with 0.2 part by weight of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) was melt-extruded using an extruder, and the thickness was 80 μm. A sheet-like transparent resin layer 4 as a transparent high crystalline polypropylene sheet was formed. Corona treatment was applied to both surfaces of the transparent resin layer 4 thus obtained, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, on one side of a 70 μm polyethylene sheet (raw fabric layer 2) that has a concealing property, a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) is hindered amine light stable against the binder resin content of the ink. A pattern printing layer 3a is provided by printing with a gravure printing method using an ink to which 0.5% by weight of an agent (Kimasorb 944; manufactured by BASF) is added, and the other side of the original fabric layer 2 is provided. Primer coating was applied. Thereafter, an adhesive for dry lamination (Takelac A540; made by Mitsui Chemicals; coating amount 2 g / m ² ) is used on the surface of the pattern layer 3a of the original fabric layer 2 with the transparent resin layer 4 as the adhesive layer 7. And bonded together by a dry laminating method. The embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the bonded sheet, and then a two-component urethane top coat (W184; manufactured by DIC Graphics) is applied at a coating thickness of 3 g / m ² to form a top coat. Layer 5 was formed. Thus, a decorative sheet 1 of this example having a total thickness of 154 μm was obtained.

<Example 6-2>
In Example 6-2, the decorative sheet 1 was provided with the top coat layer 5 and the transparent resin layer 4 each containing the zinc oxide liposome prepared in <Preparation 1 of inorganic ultraviolet absorbent vesicle> described above.

Specifically, 0.05 parts by weight of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF), 0.2 parts by weight of zinc oxide liposomes, a hindered amine light stabilizer (Kimasorb) 944; manufactured by BASF) was melt extruded using an extruder to form a sheet-like transparent resin layer 4 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. did. Corona treatment was applied to both surfaces of the transparent resin layer 4 thus obtained, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, on one side of a 70 μm polyethylene sheet (raw fabric layer 2) that has a concealing property, a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) is hindered amine light stable against the binder resin content of the ink. A pattern printing layer 3a is provided by printing with a gravure printing method using an ink to which 0.5% by weight of an agent (Kimasorb 944; manufactured by BASF) is added, and the other side of the original fabric layer 2 is provided. Primer coating was applied. Thereafter, an adhesive for dry lamination (Takelac A540; made by Mitsui Chemicals; coating amount 2 g / m ² ) is used on the surface of the pattern layer 3a of the original fabric layer 2 with the transparent resin layer 4 as the adhesive layer 7. And bonded together by a dry laminating method. After embossed pattern 4a is applied to the surface of transparent resin layer 4 of the bonded sheet, 0.1 part by weight of zinc oxide is added to 100 parts by weight of two-component urethane topcoat (W184; manufactured by DIC Graphics). A top coat coating solution to which zinc oxide liposomes were added was applied at a coating thickness of 3 g / m ² to provide a top coat layer 5, and the top coat coating solution was embedded by wiping into the recesses of the embossed pattern 4 a to obtain a total thickness of 156 μm. The decorative sheet of this example was obtained.

<Comparative Example 6-1>
In Comparative Example 6-1, a decorative sheet provided with a transparent resin layer 4 containing zinc oxide as an inorganic ultraviolet absorber that was not vesicled.

Specifically, 0.05 parts by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF), 0.2 parts by weight of zinc oxide, and a hindered amine light stabilizer (Kimasorb 944) are homopolypropylene resin. Resin manufactured by BASF) was melt-extruded using an extruder to form a sheet-like transparent resin layer 4 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. A decorative sheet was obtained in the same manner as in Example 6-1 except for the above.

<Comparative Example 6-2>
In Comparative Example 6-2, the decorative sheet was provided with the transparent resin layer 4 containing the inorganic ultraviolet absorber that was nano-processed by the solid phase method.

Specifically, zinc oxide that was nano-sized by a solid phase method was used as the inorganic ultraviolet absorber. Specifically, 100 g of isopropyl alcohol and 50 g of zinc oxide were obtained using a 30 μm stabilized zirconia bead for 60 minutes in a bead mill to obtain a zinc oxide subjected to nano-treatment with an average particle diameter of about 1 nm to 150 nm. 0.05 parts by weight of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF) on a homopolypropylene resin, and 0.2 parts by weight of zinc oxide subjected to nano-treatment obtained by the above-described solid phase method A resin as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm is obtained by melt-extruding a resin to which 0.2 part by weight of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) is added using an extruder. A decorative sheet was obtained in the same manner as in Example 6-1 except that the transparent resin layer 4 was formed into a film.

<Comparative Example 6-3>
In Comparative Example 6-3, the decorative sheet was provided with the transparent resin layer 4 containing a benzotriazole-based material as a non-vesicled UV absorber.

Specifically, 0.05 parts by weight of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF) and 0.2 parts by weight of a benzotriazole-based ultraviolet absorber (manufactured by BASF) in a homopolypropylene resin, A resin to which 0.2 parts by weight of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) was added was melt-extruded using an extruder to form a sheet as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. A decorative sheet was obtained in the same manner as in Example 6-1 except that the transparent resin layer 4 was formed.

<Evaluation>
For each decorative sheet 1 of Examples 6-1 and 6-2 and Comparative Examples 6-1 to 6-3 obtained by the above method, the ultraviolet absorbing ability and haze value were the same as in the first embodiment. The color change (ΔE) and the appearance change after the weather resistance test were evaluated. Table 13 shows the obtained evaluation results. Note that the meaning of the sign of appearance change is the same as in the first embodiment.

In the decorative sheet 1 in Example 6-1, as shown in Table 13, the decorative sheet 1 including the transparent resin layer 4 in which the amount of zinc oxide liposome added was 0.1 to 5.0 parts by weight. Because of its extremely low UV absorption value, the UV absorption performance remains almost unchanged before and after the weather resistance test, and high transparency is maintained from the haze value after the weather resistance test. You can see that Furthermore, from the value of the color difference (ΔE) before and after the weather resistance test, almost no color change was observed, and good results were also obtained in the visual appearance change evaluation, which is high over a long period of time. It became clear that it is the decorative sheet 1 which can implement | achieve a weather resistance and the outstanding design property.

However, the decorative sheet 1 provided with the transparent resin layer 4 having a zinc oxide liposome content of 0.05 part by weight in Example 6-1 has a small haze value, a value of ultraviolet absorbing ability and a weather resistance test. The value of the color difference (ΔE) before and after shows a large value. This is because the amount of zinc oxide liposome added is very small, and the white turbidity of the resin composition due to the additive is small, but sufficient UV absorption performance is not obtained and the resin material is deteriorated and decolored. is there. Therefore, the decorative sheet 1 including the transparent resin layer 4 to which zinc oxide liposomes are added at a ratio of 0.05 part by weight is extremely excellent in design and does not require high weather resistance compared to outdoor applications. Application to is possible.

Further, the decorative sheet 1 provided with the transparent resin layer 4 in which the amount of zinc oxide liposome added in Example 6-1 was 15.0 parts by weight had a large haze value, a value of ultraviolet absorbing ability and a weather resistance test. The front and rear color difference (ΔE) is a small value. This is because, since the amount of zinc oxide liposomes added is too large, the resin composition caused by the additive is largely clouded, but high UV absorption performance is obtained, and deterioration of the resin material is suppressed. It is. Therefore, the decorative sheet 1 including the transparent resin layer 4 to which zinc oxide liposomes are added at a ratio of 15.0 parts by weight can be applied to applications where the transparent resin layer 4 does not require high transparency.

From the results of Example 6-1, it was found that the transparent resin layer 4 preferably contains zinc oxide liposomes in the range of 0.1 to 5.0 parts by weight.

As shown in Table 13, the decorative sheet 1 in Example 6-2 is a decorative sheet 1 having a top coat layer 5 and a transparent resin layer 4 to which zinc oxide liposomes are added, and has an ultraviolet absorbing ability. It can be seen that the value of is very small, and the ultraviolet absorption performance almost unchanged before and after the weather resistance test is maintained. Moreover, high transparency was maintained from the haze value after a weather resistance test. Furthermore, the color difference (ΔE) before and after the weather resistance test was almost unchanged, and good results were also obtained in visual appearance change evaluation. From this evaluation result, the transparent layer composed of the top coat layer 5 and the transparent resin layer 4 can continue to exhibit excellent ultraviolet absorption performance over a long period of time. It became clear that it was possible to prevent whitening and maintain excellent transparency over a long period of time.

In the decorative sheets 1 in Comparative Examples 6-1 to 6-3, the value of the ultraviolet absorbing ability was large, and a difference was observed in the ultraviolet absorbing ability before and after the weather resistance test. Also, the haze value was large except for Comparative Example 6-3 using an organic ultraviolet absorber, and transparency was impaired. From the evaluation results of the color difference (ΔE) before and after the weather resistance test and the visual appearance change after the weather resistance test, whitening and cracks were observed, and the decorative sheets 1 of Comparative Examples 6-1 to 6-3 were inferior in weather resistance. It became clear that.

From the above results, it was clarified that the decorative sheets of Examples 6-1 and 6-2 are decorative sheets 1 having excellent weather resistance and transparency required for the decorative sheet.

From the evaluation results of the decorative sheet 1 in Examples 6-1 and 6-2 and Comparative Examples 6-1 to 6-3, the top coat layer 5 containing zinc oxide liposomes as the inorganic ultraviolet absorbent vesicle and the transparent It became clear that the decorative sheet 1 having at least one of the resin layers 4 can provide a decorative sheet having excellent weather resistance over a long period of time.

<Preparation of inorganic ultraviolet absorber vesicle 2>
A method for preparing the inorganic ultraviolet absorbent vesicle used in Examples 6-3 and 6-4 will be described. A supercritical reverse phase evaporation method was used for the preparation of the inorganic ultraviolet absorber vesicle.
Specifically, 100 parts by weight of hexane, 70 parts by weight of zinc oxide (average particle size 20 nm) as an inorganic ultraviolet absorber, and phosphatidylcholine 5 as phospholipid with respect to a high-pressure stainless steel container kept at 60 ° C. Into a supercritical state by injecting carbon dioxide so that the pressure in the container is 20 MPa, 100 parts by weight of ethyl acetate is injected while maintaining vigorous stirring and mixing, and the temperature and pressure are maintained. Then, after stirring and mixing for 15 minutes, carbon dioxide was discharged to return to atmospheric pressure. Thus, a zinc oxide liposome having a monolayer outer membrane made of phospholipid was obtained.

<Example 6-3>
In Example 6-3, the decorative sheet 1 was provided with the top coat layer 5 to which the zinc oxide liposome prepared in <Preparation 2 of inorganic ultraviolet absorber vesicle> described above was added. The added amount of the zinc oxide liposome is 0.05, 0.54, 1.07, 5.35, 10.70, 21. with respect to 100 parts by weight of the resin material which is the main component of the top coat layer 5. The amount was 40, 42.80 parts by weight. In addition, among the said addition amount, the addition amount of zinc oxide was 0.05, 0.5, 1.0, 5.0, 10.0, 20.0, 40.0 weight part.

Specifically, 0.05 part by weight of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) are added to a highly crystalline homopolypropylene resin. The resin added with 0.2 parts by weight was melt-extruded using an extruder to form a sheet-like transparent resin layer 4 as a transparent highly crystalline polypropylene sheet having a thickness of 80 μm. Corona treatment was applied to both surfaces of the transparent resin layer 4 thus obtained, and the wetting tension on the sheet surface was set to 40 dyn / cm or more. On the other hand, on one side of a 70 μm polyethylene sheet (raw fabric layer 2) having a concealing property, pattern printing is performed by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.). The pattern layer 3a was provided, and a 1 μm primer coat was applied to the other surface of the original fabric layer 2. After that, the transparent resin layer 4 is dried on the surface of the pattern layer 3a of the original fabric layer ² via a dry laminate adhesive (Takelac A540; manufactured by Mitsui Chemicals; application amount 2 g / m ² ) having a thickness of 3 μm. The laminated resin sheet was laminated to obtain a laminated resin sheet having a thickness of 157 μm comprising the raw fabric layer 2, the pattern layer 3a, the trilaminate adhesive (adhesive layer 7), the primer coat and the transparent resin layer 4. After the embossed pattern 4a is applied to the surface of the transparent resin layer 4 of the laminated resin sheet, the supercritical reverse phase evaporation method described above is applied to 100 parts by weight of a two-component urethane topcoat (W184; manufactured by DIC Graphics). The zinc oxide liposome obtained by the above was added at a ratio of 0.05, 0.54, 1.07, 5.35, 10.70, 21.40 or 42.80 parts by weight to give a coating thickness of 3 g / m ² . The top coat layer 5 was formed by coating. Thus, a decorative sheet 1 of this example having a total thickness of 160 μm was obtained.

<Example 6-4>
In Example 6-4, the top coat layer 5 added with the zinc oxide liposome prepared in <Preparation 2 of inorganic ultraviolet absorber vesicle> described above and the pattern layer 3a added with a light stabilizer were provided. A decorative sheet 1 was obtained. The amount of zinc oxide liposome added was 1.07, 5.35, and 10.70 parts by weight with respect to 100 parts by weight of the resin material as the main component of the topcoat layer 5. In addition, among the said addition amount, the addition amount of zinc oxide was 1.0, 5.0, 10.0 weight part.

Specifically, an ink obtained by adding 0.5% by weight of a hindered amine light stabilizer (Kimasorb 944; manufactured by BASF) to a binder resin component composed of a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.). A decorative sheet 1 was obtained in the same manner as in Example 6-3 except that the pattern layer 3a was formed using

<Comparative Example 6-4>
In Comparative Example 6-4, the decorative sheet 1 was provided with the top coat layer 5 containing zinc oxide that was not vesicled. The amount of zinc oxide added was set to 0.5 or 1.0 part by weight with respect to 100 parts by weight of the resin material that is the main component of the topcoat layer 5. The topcoat layer 5 has the same configuration as that of the decorative sheet 1 described in Example 6-3 except that the configuration is as described above.

<Comparative Example 6-5>
In Comparative Example 6-5, the decorative sheet 1 was provided with the top coat layer 5 to which the nano-ized zinc oxide that had been nano-processed by the solid phase method was added. In addition, the addition amount of nano-ized zinc oxide was 0.5 or 1.0 part by weight with respect to 100 parts by weight of the resin material which is the main component of the top coat layer 5. The topcoat layer 5 has the same configuration as that of the decorative sheet 1 described in Example 6-3 except that the configuration is as described above.

<Comparative Example 6-6>
In Comparative Example 6-6, the decorative sheet 1 was provided with a top coat layer 5 to which a triazine-based UV absorber that is an organic UV absorber was added. The addition amount of the triazine-based ultraviolet absorber was 0.5 parts by weight with respect to 100 parts by weight of the resin material which is the main component of the top coat layer 5. The topcoat layer 5 has the same configuration as that of the decorative sheet 1 described in Example 6-3 except that the configuration is as described above.

<Comparative Example 6-7>
In Comparative Example 6-7, the decorative sheet 1 was provided with the top coat layer 5 and the transparent resin layer 4 to which no inorganic ultraviolet absorber was added. Other configurations are the same as those of the decorative sheet 1 described in Example 6-3.

For each decorative sheet 1 of Examples 6-3 and 6-4 and Comparative Examples 6-4 to 6-7, as in Examples 6-1 and 6-2 and Comparative Examples 6-1 to 6-3 (That is, in the same manner as in the first embodiment), calculation of ultraviolet absorbing ability, measurement of haze value after weather resistance test, calculation of color difference (ΔE) of each decorative sheet 1 before and after the weather resistance test, and after weather resistance test The appearance change was evaluated. The contents of the appearance change symbols are also the same as in Examples 6-1 and 6-2 and Comparative Examples 6-1 to 6-3 (that is, the same as in the first embodiment). Table 14 shows the obtained evaluation results.

In the decorative sheet 1 in Example 6-3, as shown in Table 14, the decorative sheet 1 including the top coat layer 5 in which the amount of zinc oxide liposome added was 0.54 to 21.40 parts by weight. For UV, the value of UV absorption and the color difference (ΔE) before and after the weather resistance test are small, and a haze value of 15% or less is realized even after the weather resistance test, providing excellent transparency over a long period of time. It was revealed that the decorative sheet 1 can be maintained. Of the added amount of the zinc oxide liposome, zinc oxide was 0.50 to 20.00 parts by weight.

However, the decorative sheet 1 provided with the topcoat layer 5 in which the amount of zinc oxide liposome added in Example 6-3 is 0.05 parts by weight has a small haze value, a value of ultraviolet absorbing ability and a weather resistance test. The value of the color difference (ΔE) before and after shows a large value. This is because the amount of zinc oxide liposome added is very small, and the white turbidity of the resin composition due to the additive is small, but sufficient UV absorption performance is not obtained and the resin material is deteriorated and decolored. is there. Therefore, the decorative sheet 1 including the top coat layer 5 in which the zinc oxide liposome is added at a ratio of 0.05 part by weight with respect to 100 parts by weight of the resin material as the main component is extremely excellent in design, and is used outdoors. It can be applied to indoor applications where high weather resistance is not required. In addition, zinc oxide was 0.05 weight part among the addition amount of the said zinc oxide liposome. Further, other contained components were very small and out of the effective number range.

Further, the decorative sheet 1 provided with the top coat layer 5 in which the amount of zinc oxide liposome added in Example 6-3 was 42.80 parts by weight had a large haze value, a value of ultraviolet absorbing ability and a weather resistance test. The front and rear color difference (ΔE) is a small value. This is because, since the amount of zinc oxide liposomes added is too large, the resin composition caused by the additive is largely clouded, but high UV absorption performance is obtained, and deterioration of the resin material is suppressed. It is. Therefore, the decorative sheet 1 including the top coat layer 5 in which the zinc oxide liposome is added at a ratio of 42.80 parts by weight with respect to 100 parts by weight of the resin material as the main component requires the top coat layer 5 to have high transparency. Application to unusable applications is conceivable. In addition, zinc oxide was 40.00 weight part among the addition amount of the said zinc oxide liposome.

From the result of Example 6-3, it was revealed that it is preferable to add the zinc oxide liposome within the range of 0.54 to 21.40 parts by weight to the topcoat layer 5. Of the added amount of the zinc oxide liposome, zinc oxide was 0.5 to 20.00 parts by weight.

In the decorative sheet 1 in Example 6-4, as shown in Table 14, the decorative sheet 1 includes a top coat layer 5 to which zinc oxide liposomes are added and a pattern layer 3a containing a light stabilizer. As for the value of the ultraviolet absorptivity, the smaller the amount of zinc oxide liposome added, the smaller the value. Moreover, in the case of all the addition amount, the value of the haze value after a weather resistance test was small, and high transparency was maintained. Furthermore, the color difference (ΔE) before and after the weather resistance test was almost unchanged, and good results were also obtained in visual appearance change evaluation. From this evaluation result, in the decorative sheets 1 of Examples 6-3 and 6-4, it is possible to continue to exhibit excellent ultraviolet absorption performance over a long period as the addition amount of the zinc oxide liposome is increased. Thus, it has been clarified that the excellent ultraviolet absorption performance prevents the resin from fading and whitening, and can maintain excellent transparency over a long period of time. Furthermore, since the decorative sheet 1 in Example 6-4 is a pattern layer 3a to which a light stabilizer is added, the amount of zinc oxide liposomes added in Example 6-3 is 1.07 parts by weight or more. Compared with the decorative sheet 1 having the top coat layer 5 of 10.70 parts by weight, the color difference (ΔE) before and after the weather resistance test is extremely small, and the pattern layer is formed by the light stabilizer. It became clear that the decorative sheet which can suppress the decoloring of 3a and can realize a colorful design for a longer period of time is obtained.

As shown in Table 14, it can be seen that the decorative sheet 1 in Comparative Examples 6-4 and 6-5 has a UV absorbing performance that is small in the value of UV absorbing ability and does not change within the test time. However, it can be seen that the haze value after the weather resistance test is large and the transparency of the transparent layer is poor. Moreover, whitening and a crack were recognized from the color difference ((DELTA) E) after a weather resistance test, and the external appearance change evaluation result after a weather resistance test. From this evaluation result, it was revealed that the decorative sheets 1 of Comparative Examples 6-4 and 6-5 were inferior in design and weather resistance.

Further, in the decorative sheet 1 in Comparative Example 6-6, as shown in Table 14, the value of the ultraviolet absorbing ability is large, and the weather resistance is evaluated based on the color difference (ΔE) after the weather resistance test and the evaluation result of the visual appearance change. It turns out that it is inferior to. About a haze value, the small value is shown and it turns out that it has the outstanding transparency. From this evaluation result, it became clear that the organic ultraviolet absorber is inferior in ultraviolet absorption performance over a long period of time, although it can maintain high transparency of the transparent layer.

In the decorative sheet 1 in Comparative Example 6-7, as shown in Table 14, the haze value after the weather resistance test is low, and the transparent layer composed of the top coat layer 5 and the transparent resin layer 4 is It can be seen that excellent transparency is maintained. However, the value of the UV absorbing ability is very large, and from the color difference (ΔE) after the weather resistance test and the evaluation result of the appearance change by visual observation, remarkable fading is recognized in the pattern layer 3a provided under the transparent layer. It was. From this evaluation result, it became clear that the decorative sheet 1 to which the ultraviolet absorber is not added is inferior in weather resistance to the top coat layer 5 and the transparent resin layer 4.

From the above evaluation results of the decorative sheet 1 in Examples 6-3 and 6-4 and Comparative Examples 6-4 to 6-7, in particular, a resin material mainly composed of zinc oxide liposomes as an inorganic ultraviolet absorbent vesicle By making the decorative sheet 1 provided with the top coat layer 5 added at a ratio of 0.54 parts by weight to 21.40 parts by weight with respect to 100 parts by weight, the weather resistance is further improved over a longer period of time. It can be seen that a decorative sheet having excellent properties can be provided.

[Reference example]
Hereinafter, a decorative sheet other than the decorative sheet described in the present embodiment will be briefly described as a reference example of the present invention.
In a decorative sheet other than the decorative sheet described in the present embodiment, when an organic ultraviolet absorber such as triazine is added to the topcoat layer 5, the transparency of the base resin can be maintained, but a change with time cannot be avoided. There was a problem in the sustainability of UV absorption performance over a long period of time. Based on this, when an inorganic ultraviolet absorber with little secular change is used, opaque particles are aggregated and transparency is lowered, which may impair the design of the decorative sheet itself.

Further, when the blending amount of the ultraviolet absorber is increased in order to improve the weather resistance, the ultraviolet absorber aggregates in the resin and bleed-out occurs, which may cause stickiness on the sheet surface and a decrease in adhesion.
In addition, when an embossed pattern is formed to improve the design of the decorative sheet, the recessed portion of the embossed pattern is thinner than other portions, so the weather resistance is particularly low, and deterioration occurs from the recessed portion. Could begin to whiten or break.

As a result of intensive studies, the present inventors have succeeded in dramatically improving the dispersibility of the inorganic ultraviolet absorber in the resin material by including the inorganic ultraviolet absorber in a state of being included in the vesicle. It has been found that the transparency required for the decorative sheet can be achieved.
The decorative sheet 1 of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Original fabric layer 3 Ink layer 3a Picture pattern layer 3b Solid ink layer 4 Transparent resin layer 4a Embossed pattern 4b Adhesive resin layer 5 Topcoat layer 6 Primer layer 7 Adhesive layer 8 Concealing layer B Base material

Claims (20)

A decorative sheet comprising a topcoat layer on the outermost layer and a transparent resin layer on the lower layer of the topcoat layer,
An organic ultraviolet absorber and an inorganic ultraviolet absorber are added to at least one of the topcoat layer and the transparent resin layer,
The organic ultraviolet absorbent and the inorganic ultraviolet absorbent are an organic ultraviolet absorbent vesicle and an inorganic ultraviolet absorbent vesicle separately encapsulated in a vesicle having a single-layer outer film, respectively. A decorative sheet. A decorative sheet comprising a topcoat layer on the outermost layer and a transparent resin layer on the lower layer of the topcoat layer,
An organic ultraviolet absorber and an inorganic ultraviolet absorber are added to at least one of the topcoat layer and the transparent resin layer,
Cosmetics characterized in that the organic ultraviolet absorber and the inorganic ultraviolet absorber are organic / inorganic ultraviolet absorber vesicles encapsulated in a vesicle having a single-layer outer membrane. Sheet. A decorative sheet comprising a topcoat layer on the outermost layer and a transparent resin layer on the lower layer of the topcoat layer,
Any one of the topcoat layer and the transparent resin layer contains an organic ultraviolet absorber and an inorganic ultraviolet absorber,
Either one of the organic ultraviolet absorbent and the inorganic ultraviolet absorbent is an organic ultraviolet absorbent vesicle or an inorganic ultraviolet absorbent vesicle encapsulated in a vesicle having a single-layer outer membrane. Characteristic decorative sheet. The other resin layer not selected in claim 3 contains at least one of the organic ultraviolet absorber or the inorganic ultraviolet absorber,
4. One of the contained ultraviolet absorbers is an organic ultraviolet absorber vesicle or an inorganic ultraviolet absorber vesicle encapsulated in a vesicle having a single-layer outer membrane. Makeup sheet. The decorative sheet according to any one of claims 1 to 4, wherein the outer membrane of the vesicle is made of phospholipid. 6. The organic ultraviolet absorber according to claim 1, wherein the organic ultraviolet absorber is at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate. Makeup sheet. The decorative sheet according to any one of claims 1 to 6, wherein the inorganic ultraviolet absorber is zinc oxide. An embossed pattern is formed on the surface of the transparent resin layer on the topcoat layer side,
The decorative sheet according to any one of claims 1 to 7, wherein the top coat layer is embedded in the recess of the embossed pattern. A decorative sheet comprising a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer,
The top coat layer and the transparent resin layer contain an organic ultraviolet absorber,
A decorative sheet, wherein the organic ultraviolet absorber is an organic ultraviolet absorber vesicle contained in an outer membrane. The decorative sheet according to claim 9, wherein the outer membrane is a single layer membrane. An embossed pattern is formed on the surface of the transparent resin layer on the topcoat layer side,
The decorative sheet according to claim 9 or 10, wherein the top coat layer is embedded in the embossed recess. A decorative sheet comprising a transparent resin layer made of a transparent olefin resin,
The transparent resin layer contains an organic ultraviolet absorber,
A decorative sheet, wherein the organic ultraviolet absorbent is an organic ultraviolet absorbent vesicle having an outer film made of a single layer film. The cosmetic sheet according to any one of claims 9 to 12, wherein the organic ultraviolet absorbent vesicle is an organic ultraviolet absorbent liposome having an outer membrane made of phospholipid. The organic ultraviolet absorber is at least one of benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate, according to any one of claims 9 to 13. Makeup sheet. A decorative sheet comprising a top coat layer on the outermost layer and a transparent resin layer on the lower surface of the top coat layer,
At least one of the top coat layer and the transparent resin layer contains an inorganic ultraviolet absorber,
A decorative sheet, wherein the inorganic ultraviolet absorbent is an inorganic ultraviolet absorbent vesicle contained in an outer membrane. The decorative sheet according to claim 15, wherein the outer membrane is a single layer membrane. The decorative sheet according to claim 15 or 16, wherein the inorganic ultraviolet absorbent vesicle is an inorganic ultraviolet absorbent liposome having an outer membrane made of phospholipid. The decorative sheet according to any one of claims 15 to 17, wherein the inorganic ultraviolet absorber is zinc oxide. An embossed pattern is formed on the transparent resin layer,
The decorative sheet according to any one of claims 15 to 18, wherein the topcoat layer is embedded in at least a concave portion of the embossed pattern. The decorative sheet according to any one of claims 9 to 19, wherein an ink layer containing a light stabilizer is provided under the transparent resin layer.

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